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Atomic orbital | Bohr atom | Bohr atom
In 1909, Ernest Rutherford discovered that the bulk of the atomic mass was tightly condensed into a nucleus, which was also found to be positively charged. It became clear from his analysis in 1911 that the plum pudding model could not explain atomic structure. In 1913, Rutherford's post-doctoral student, Niels Bohr, proposed a new model of the atom, wherein electrons orbited the nucleus with classical periods, but were permitted to have only discrete values of angular momentum, quantized in units ħ. This constraint automatically allowed only certain electron energies. The Bohr model of the atom fixed the problem of energy loss from radiation from a ground state (by declaring that there was no state below this), and more importantly explained the origin of spectral lines.
thumb|The Rutherford–Bohr model of the hydrogen atom
After Bohr's use of Einstein's explanation of the photoelectric effect to relate energy levels in atoms with the wavelength of emitted light, the connection between the structure of electrons in atoms and the emission and absorption spectra of atoms became an increasingly useful tool in the understanding of electrons in atoms. The most prominent feature of emission and absorption spectra (known experimentally since the middle of the 19th century), was that these atomic spectra contained discrete lines. The significance of the Bohr model was that it related the lines in emission and absorption spectra to the energy differences between the orbits that electrons could take around an atom. This was, however, not achieved by Bohr through giving the electrons some kind of wave-like properties, since the idea that electrons could behave as matter waves was not suggested until eleven years later. Still, the Bohr model's use of quantized angular momenta and therefore quantized energy levels was a significant step toward the understanding of electrons in atoms, and also a significant step towards the development of quantum mechanics in suggesting that quantized restraints must account for all discontinuous energy levels and spectra in atoms.
With de Broglie's suggestion of the existence of electron matter waves in 1924, and for a short time before the full 1926 Schrödinger equation treatment of hydrogen-like atoms, a Bohr electron "wavelength" could be seen to be a function of its momentum; so a Bohr orbiting electron was seen to orbit in a circle at a multiple of its half-wavelength. The Bohr model for a short time could be seen as a classical model with an additional constraint provided by the 'wavelength' argument. However, this period was immediately superseded by the full three-dimensional wave mechanics of 1926. In our current understanding of physics, the Bohr model is called a semi-classical model because of its quantization of angular momentum, not primarily because of its relationship with electron wavelength, which appeared in hindsight a dozen years after the Bohr model was proposed.
The Bohr model was able to explain the emission and absorption spectra of hydrogen. The energies of electrons in the n = 1, 2, 3, etc. states in the Bohr model match those of current physics. However, this did not explain similarities between different atoms, as expressed by the periodic table, such as the fact that helium (two electrons), neon (10 electrons), and argon (18 electrons) exhibit similar chemical inertness. Modern quantum mechanics explains this in terms of electron shells and subshells which can each hold a number of electrons determined by the Pauli exclusion principle. Thus the n = 1 state can hold one or two electrons, while the n = 2 state can hold up to eight electrons in 2s and 2p subshells. In helium, all n = 1 states are fully occupied; the same is true for n = 1 and n = 2 in neon. In argon, the 3s and 3p subshells are similarly fully occupied by eight electrons; quantum mechanics also allows a 3d subshell but this is at higher energy than the 3s and 3p in argon (contrary to the situation for hydrogen) and remains empty. |
Atomic orbital | Modern conceptions and connections to the Heisenberg uncertainty principle | Modern conceptions and connections to the Heisenberg uncertainty principle
Immediately after Heisenberg discovered his uncertainty principle, Bohr noted that the existence of any sort of wave packet implies uncertainty in the wave frequency and wavelength, since a spread of frequencies is needed to create the packet itself. In quantum mechanics, where all particle momenta are associated with waves, it is the formation of such a wave packet which localizes the wave, and thus the particle, in space. In states where a quantum mechanical particle is bound, it must be localized as a wave packet, and the existence of the packet and its minimum size implies a spread and minimal value in particle wavelength, and thus also momentum and energy. In quantum mechanics, as a particle is localized to a smaller region in space, the associated compressed wave packet requires a larger and larger range of momenta, and thus larger kinetic energy. Thus the binding energy to contain or trap a particle in a smaller region of space increases without bound as the region of space grows smaller. Particles cannot be restricted to a geometric point in space, since this would require infinite particle momentum.
In chemistry, Erwin Schrödinger, Linus Pauling, Mulliken and others noted that the consequence of Heisenberg's relation was that the electron, as a wave packet, could not be considered to have an exact location in its orbital. Max Born suggested that the electron's position needed to be described by a probability distribution which was connected with finding the electron at some point in the wave-function which described its associated wave packet. The new quantum mechanics did not give exact results, but only the probabilities for the occurrence of a variety of possible such results. Heisenberg held that the path of a moving particle has no meaning if we cannot observe it, as we cannot with electrons in an atom.
In the quantum picture of Heisenberg, Schrödinger and others, the Bohr atom number n for each orbital became known as an n-sphere in a three-dimensional atom and was pictured as the most probable energy of the probability cloud of the electron's wave packet which surrounded the atom. |
Atomic orbital | Orbital names | Orbital names |
Atomic orbital | Orbital notation and subshells | Orbital notation and subshells
Orbitals have been given names, which are usually given in the form:
where X is the energy level corresponding to the principal quantum number ; type is a lower-case letter denoting the shape or subshell of the orbital, corresponding to the angular momentum quantum number .
For example, the orbital 1s (pronounced as the individual numbers and letters: "'one' 'ess'") is the lowest energy level () and has an angular quantum number of , denoted as s. Orbitals with are denoted as p, d and f respectively.
The set of orbitals for a given n and is called a subshell, denoted
.
The superscript y shows the number of electrons in the subshell. For example, the notation 2p4 indicates that the 2p subshell of an atom contains 4 electrons. This subshell has 3 orbitals, each with n = 2 and = 1. |
Atomic orbital | X-ray notation | X-ray notation
There is also another, less common system still used in X-ray science known as X-ray notation, which is a continuation of the notations used before orbital theory was well understood. In this system, the principal quantum number is given a letter associated with it. For , the letters associated with those numbers are K, L, M, N, O, ... respectively. |
Atomic orbital | Hydrogen-like orbitals | Hydrogen-like orbitals
The simplest atomic orbitals are those that are calculated for systems with a single electron, such as the hydrogen atom. An atom of any other element ionized down to a single electron (He+, Li2+, etc.) is very similar to hydrogen, and the orbitals take the same form. In the Schrödinger equation for this system of one negative and one positive particle, the atomic orbitals are the eigenstates of the Hamiltonian operator for the energy. They can be obtained analytically, meaning that the resulting orbitals are products of a polynomial series, and exponential and trigonometric functions. (see hydrogen atom).
For atoms with two or more electrons, the governing equations can be solved only with the use of methods of iterative approximation. Orbitals of multi-electron atoms are qualitatively similar to those of hydrogen, and in the simplest models, they are taken to have the same form. For more rigorous and precise analysis, numerical approximations must be used.
A given (hydrogen-like) atomic orbital is identified by unique values of three quantum numbers: , , and . The rules restricting the values of the quantum numbers, and their energies (see below), explain the electron configuration of the atoms and the periodic table.
The stationary states (quantum states) of a hydrogen-like atom are its atomic orbitals. However, in general, an electron's behavior is not fully described by a single orbital. Electron states are best represented by time-depending "mixtures" (linear combinations) of multiple orbitals. See Linear combination of atomic orbitals molecular orbital method.
The quantum number first appeared in the Bohr model where it determines the radius of each circular electron orbit. In modern quantum mechanics however, determines the mean distance of the electron from the nucleus; all electrons with the same value of n lie at the same average distance. For this reason, orbitals with the same value of n are said to comprise a "shell". Orbitals with the same value of n and also the same value of are even more closely related, and are said to comprise a "subshell". |
Atomic orbital | Quantum numbers | Quantum numbers
Because of the quantum mechanical nature of the electrons around a nucleus, atomic orbitals can be uniquely defined by a set of integers known as quantum numbers. These quantum numbers occur only in certain combinations of values, and their physical interpretation changes depending on whether real or complex versions of the atomic orbitals are employed. |
Atomic orbital | Complex orbitals | Complex orbitals
thumb|450px|alt=Electronic levels|Energetic levels and sublevels of polyelectronic atoms
In physics, the most common orbital descriptions are based on the solutions to the hydrogen atom, where orbitals are given by the product between a radial function and a pure spherical harmonic. The quantum numbers, together with the rules governing their possible values, are as follows:
The principal quantum number describes the energy of the electron and is always a positive integer. In fact, it can be any positive integer, but for reasons discussed below, large numbers are seldom encountered. Each atom has, in general, many orbitals associated with each value of n; these orbitals together are sometimes called electron shells.
The azimuthal quantum number describes the orbital angular momentum of each electron and is a non-negative integer. Within a shell where is some integer , ranges across all (integer) values satisfying the relation . For instance, the shell has only orbitals with , and the shell has only orbitals with , and . The set of orbitals associated with a particular value of are sometimes collectively called a subshell.
The magnetic quantum number, , describes the projection of the orbital angular momentum along a chosen axis. It determines the magnitude of the current circulating around that axis and the orbital contribution to the magnetic moment of an electron via the Ampèrian loop model. Within a subshell , obtains the integer values in the range .
The above results may be summarized in the following table. Each cell represents a subshell, and lists the values of available in that subshell. Empty cells represent subshells that do not exist.
... ... 0 −1, 0, 1 ... 0 −1, 0, 1 −2, −1, 0, 1, 2 ... 0 −1, 0, 1 −2, −1, 0, 1, 2 −3, −2, −1, 0, 1, 2, 3 ... 0 −1, 0, 1 −2, −1, 0, 1, 2 −3, −2, −1, 0, 1, 2, 3 −4, −3, −2, −1, 0, 1, 2, 3, 4 ... ... ... ... ... ... ... ...
Subshells are usually identified by their - and -values. is represented by its numerical value, but is represented by a letter as follows: 0 is represented by 's', 1 by 'p', 2 by 'd', 3 by 'f', and 4 by 'g'. For instance, one may speak of the subshell with and as a '2s subshell'.
Each electron also has angular momentum in the form of quantum mechanical spin given by spin s = . Its projection along a specified axis is given by the spin magnetic quantum number, ms, which can be + or −. These values are also called "spin up" or "spin down" respectively.
The Pauli exclusion principle states that no two electrons in an atom can have the same values of all four quantum numbers. If there are two electrons in an orbital with given values for three quantum numbers, (, , ), these two electrons must differ in their spin projection ms.
The above conventions imply a preferred axis (for example, the z direction in Cartesian coordinates), and they also imply a preferred direction along this preferred axis. Otherwise there would be no sense in distinguishing from . As such, the model is most useful when applied to physical systems that share these symmetries. The Stern–Gerlach experimentwhere an atom is exposed to a magnetic fieldprovides one such example. |
Atomic orbital | Real orbitals | Real orbitals
thumb|220px|Animation of continuously varying superpositions between the and the orbitals. This animation does not use the Condon–Shortley phase convention.
Instead of the complex orbitals described above, it is common, especially in the chemistry literature, to use real atomic orbitals. These real orbitals arise from simple linear combinations of complex orbitals. Using the Condon–Shortley phase convention, real orbitals are related to complex orbitals in the same way that the real spherical harmonics are related to complex spherical harmonics. Letting denote a complex orbital with quantum numbers , , and , the real orbitals may be defined by
If , with the radial part of the orbital, this definition is equivalent to where is the real spherical harmonic related to either the real or imaginary part of the complex spherical harmonic .
Real spherical harmonics are physically relevant when an atom is embedded in a crystalline solid, in which case there are multiple preferred symmetry axes but no single preferred direction. Real atomic orbitals are also more frequently encountered in introductory chemistry textbooks and shown in common orbital visualizations. In real hydrogen-like orbitals, quantum numbers and have the same interpretation and significance as their complex counterparts, but is no longer a good quantum number (but its absolute value is).
Some real orbitals are given specific names beyond the simple designation. Orbitals with quantum number are called orbitals. With this one can already assign names to complex orbitals such as ; the first symbol is the quantum number, the second character is the symbol for that particular quantum number and the subscript is the quantum number.
As an example of how the full orbital names are generated for real orbitals, one may calculate . From the table of spherical harmonics, with . Then
Likewise . As a more complicated example:
In all these cases we generate a Cartesian label for the orbital by examining, and abbreviating, the polynomial in appearing in the numerator. We ignore any terms in the polynomial except for the term with the highest exponent in .
We then use the abbreviated polynomial as a subscript label for the atomic state, using the same nomenclature as above to indicate the and quantum numbers.
The expression above all use the Condon–Shortley phase convention which is favored by quantum physicists. Other conventions exist for the phase of the spherical harmonics. Under these different conventions the and orbitals may appear, for example, as the sum and difference of and , contrary to what is shown above.
Below is a list of these Cartesian polynomial names for the atomic orbitals. There does not seem to be reference in the literature as to how to abbreviate the long Cartesian spherical harmonic polynomials for so there does not seem be consensus on the naming of orbitals or higher according to this nomenclature.
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Atomic orbital | Shapes of orbitals | Shapes of orbitals
thumb|Transparent cloud view of a computed 6s hydrogen orbital. The s orbitals, though spherically symmetric, have radially placed wave-nodes for . Only s orbitals invariably have a center anti-node; the other types never do.
Simple pictures showing orbital shapes are intended to describe the angular forms of regions in space where the electrons occupying the orbital are likely to be found. The diagrams cannot show the entire region where an electron can be found, since according to quantum mechanics there is a non-zero probability of finding the electron (almost) anywhere in space. Instead the diagrams are approximate representations of boundary or contour surfaces where the probability density has a constant value, chosen so that there is a certain probability (for example 90%) of finding the electron within the contour. Although as the square of an absolute value is everywhere non-negative, the sign of the wave function is often indicated in each subregion of the orbital picture.
Sometimes the function is graphed to show its phases, rather than which shows probability density but has no phase (which is lost when taking absolute value, since is a complex number). orbital graphs tend to have less spherical, thinner lobes than graphs, but have the same number of lobes in the same places, and otherwise are recognizable. This article, to show wave function phase, shows mostly graphs.
The lobes can be seen as standing wave interference patterns between the two counter-rotating, ring-resonant traveling wave and modes; the projection of the orbital onto the xy plane has a resonant wavelength around the circumference. Although rarely shown, the traveling wave solutions can be seen as rotating banded tori; the bands represent phase information. For each there are two standing wave solutions and . If , the orbital is vertical, counter rotating information is unknown, and the orbital is z-axis symmetric. If there are no counter rotating modes. There are only radial modes and the shape is spherically symmetric.
Nodal planes and nodal spheres are surfaces on which the probability density vanishes. The number of nodal surfaces is controlled by the quantum numbers and . An orbital with azimuthal quantum number has radial nodal planes passing through the origin. For example, the s orbitals () are spherically symmetric and have no nodal planes, whereas the p orbitals () have a single nodal plane between the lobes. The number of nodal spheres equals , consistent with the restriction on the quantum numbers. The principal quantum number controls the total number of nodal surfaces which is . Loosely speaking, is energy, is analogous to eccentricity, and is orientation.
In general, determines size and energy of the orbital for a given nucleus; as increases, the size of the orbital increases. The higher nuclear charge of heavier elements causes their orbitals to contract by comparison to lighter ones, so that the size of the atom remains very roughly constant, even as the number of electrons increases.
thumb|Experimentally imaged 1s and 2p core-electron orbitals of Sr, including the effects of atomic thermal vibration and excitation broadening, retrieved from energy dispersive x-ray spectroscopy (EDX) in scanning transmission electron microscopy (STEM).
Also in general terms, determines an orbital's shape, and its orientation. However, since some orbitals are described by equations in complex numbers, the shape sometimes depends on also. Together, the whole set of orbitals for a given and fill space as symmetrically as possible, though with increasingly complex sets of lobes and nodes.
The single s orbitals () are shaped like spheres. For it is roughly a solid ball (densest at center and fades outward exponentially), but for , each single s orbital is made of spherically symmetric surfaces which are nested shells (i.e., the "wave-structure" is radial, following a sinusoidal radial component as well). See illustration of a cross-section of these nested shells, at right. The s orbitals for all numbers are the only orbitals with an anti-node (a region of high wave function density) at the center of the nucleus. All other orbitals (p, d, f, etc.) have angular momentum, and thus avoid the nucleus (having a wave node at the nucleus). Recently, there has been an effort to experimentally image the 1s and 2p orbitals in a SrTiO3 crystal using scanning transmission electron microscopy with energy dispersive x-ray spectroscopy. Because the imaging was conducted using an electron beam, Coulombic beam-orbital interaction that is often termed as the impact parameter effect is included in the outcome (see the figure at right).
The shapes of p, d and f orbitals are described verbally here and shown graphically in the Orbitals table below. The three p orbitals for have the form of two ellipsoids with a point of tangency at the nucleus (the two-lobed shape is sometimes referred to as a "dumbbell"—there are two lobes pointing in opposite directions from each other). The three p orbitals in each shell are oriented at right angles to each other, as determined by their respective linear combination of values of . The overall result is a lobe pointing along each direction of the primary axes.
Four of the five d orbitals for look similar, each with four pear-shaped lobes, each lobe tangent at right angles to two others, and the centers of all four lying in one plane. Three of these planes are the xy-, xz-, and yz-planes—the lobes are between the pairs of primary axes—and the fourth has the center along the x and y axes themselves. The fifth and final d orbital consists of three regions of high probability density: a torus in between two pear-shaped regions placed symmetrically on its z axis. The overall total of 18 directional lobes point in every primary axis direction and between every pair.
There are seven f orbitals, each with shapes more complex than those of the d orbitals.
Additionally, as is the case with the s orbitals, individual p, d, f and g orbitals with values higher than the lowest possible value, exhibit an additional radial node structure which is reminiscent of harmonic waves of the same type, as compared with the lowest (or fundamental) mode of the wave. As with s orbitals, this phenomenon provides p, d, f, and g orbitals at the next higher possible value of (for example, 3p orbitals vs. the fundamental 2p), an additional node in each lobe. Still higher values of further increase the number of radial nodes, for each type of orbital.
The shapes of atomic orbitals in one-electron atom are related to 3-dimensional spherical harmonics. These shapes are not unique, and any linear combination is valid, like a transformation to cubic harmonics, in fact it is possible to generate sets where all the d's are the same shape, just like the and are the same shape.
thumb|The 1s, 2s, and 2p orbitals of a sodium atom
Although individual orbitals are most often shown independent of each other, the orbitals coexist around the nucleus at the same time. Also, in 1927, Albrecht Unsöld proved that if one sums the electron density of all orbitals of a particular azimuthal quantum number of the same shell (e.g., all three 2p orbitals, or all five 3d orbitals) where each orbital is occupied by an electron or each is occupied by an electron pair, then all angular dependence disappears; that is, the resulting total density of all the atomic orbitals in that subshell (those with the same ) is spherical. This is known as Unsöld's theorem. |
Atomic orbital | Orbitals table | Orbitals table
This table shows the real hydrogen-like wave functions for all atomic orbitals up to 7s, and therefore covers the occupied orbitals in the ground state of all elements in the periodic table up to radium and some beyond. "ψ" graphs are shown with − and + wave function phases shown in two different colors (arbitrarily red and blue). The orbital is the same as the orbital, but the and are formed by taking linear combinations of the and orbitals (which is why they are listed under the label). Also, the and are not the same shape as the , since they are pure spherical harmonics.
s ()p ()d ()f () s pz px py dz2 dxz dyz dxy dx2−y2 fz3 fxz2 fyz2 fxyz fz(x2−y2) fx(x2−3y2) fy(3x2−y2) 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px 50px . . . . . . . . . . . . . . . . . . . . . 50px 50px 50px 50px . . . ‡ . . . ‡ . . . ‡ . . . ‡ . . . ‡ . . . * . . . * . . . * . . . * . . . * . . . * . . . * 50px . . . † . . . † . . . † . . . * . . . * . . . * . . . * . . . * . . . * . . . * . . . * . . . * . . . * . . . * . . . *
* No elements with 6f, 7d or 7f electrons have been discovered yet.
† Elements with 7p electrons have been discovered, but their electronic configurations are only predicted – save the exceptional Lr, which fills 7p1 instead of 6d1.
‡ For the elements whose highest occupied orbital is a 6d orbital, only some electronic configurations have been confirmed. (Mt, Ds, Rg and Cn are still missing).
These are the real-valued orbitals commonly used in chemistry. Only the orbitals where are eigenstates of the orbital angular momentum operator, . The columns with are combinations of two eigenstates. See comparison in the following picture: thumb|Atomic orbitals spdf m-eigenstates and superpositions |
Atomic orbital | Qualitative understanding of shapes | Qualitative understanding of shapes
The shapes of atomic orbitals can be qualitatively understood by considering the analogous case of standing waves on a circular drum. To see the analogy, the mean vibrational displacement of each bit of drum membrane from the equilibrium point over many cycles (a measure of average drum membrane velocity and momentum at that point) must be considered relative to that point's distance from the center of the drum head. If this displacement is taken as being analogous to the probability of finding an electron at a given distance from the nucleus, then it will be seen that the many modes of the vibrating disk form patterns that trace the various shapes of atomic orbitals. The basic reason for this correspondence lies in the fact that the distribution of kinetic energy and momentum in a matter-wave is predictive of where the particle associated with the wave will be. That is, the probability of finding an electron at a given place is also a function of the electron's average momentum at that point, since high electron momentum at a given position tends to "localize" the electron in that position, via the properties of electron wave-packets (see the Heisenberg uncertainty principle for details of the mechanism).
This relationship means that certain key features can be observed in both drum membrane modes and atomic orbitals. For example, in all of the modes analogous to s orbitals (the top row in the animated illustration below), it can be seen that the very center of the drum membrane vibrates most strongly, corresponding to the antinode in all s orbitals in an atom. This antinode means the electron is most likely to be at the physical position of the nucleus (which it passes straight through without scattering or striking it), since it is moving (on average) most rapidly at that point, giving it maximal momentum.
A mental "planetary orbit" picture closest to the behavior of electrons in s orbitals, all of which have no angular momentum, might perhaps be that of a Keplerian orbit with the orbital eccentricity of 1 but a finite major axis, not physically possible (because particles were to collide), but can be imagined as a limit of orbits with equal major axes but increasing eccentricity.
Below, a number of drum membrane vibration modes and the respective wave functions of the hydrogen atom are shown. A correspondence can be considered where the wave functions of a vibrating drum head are for a two-coordinate system and the wave functions for a vibrating sphere are three-coordinate .
None of the other sets of modes in a drum membrane have a central antinode, and in all of them the center of the drum does not move. These correspond to a node at the nucleus for all non-s orbitals in an atom. These orbitals all have some angular momentum, and in the planetary model, they correspond to particles in orbit with eccentricity less than 1.0, so that they do not pass straight through the center of the primary body, but keep somewhat away from it.
In addition, the drum modes analogous to p and d modes in an atom show spatial irregularity along the different radial directions from the center of the drum, whereas all of the modes analogous to s modes are perfectly symmetrical in radial direction. The non-radial-symmetry properties of non-s orbitals are necessary to localize a particle with angular momentum and a wave nature in an orbital where it must tend to stay away from the central attraction force, since any particle localized at the point of central attraction could have no angular momentum. For these modes, waves in the drum head tend to avoid the central point. Such features again emphasize that the shapes of atomic orbitals are a direct consequence of the wave nature of electrons. |
Atomic orbital | Orbital energy | Orbital energy
In atoms with one electron (hydrogen-like atom), the energy of an orbital (and, consequently, any electron in the orbital) is determined mainly by . The orbital has the lowest possible energy in the atom. Each successively higher value of has a higher energy, but the difference decreases as increases. For high , the energy becomes so high that the electron can easily escape the atom. In single electron atoms, all levels with different within a given are degenerate in the Schrödinger approximation, and have the same energy. This approximation is broken slightly in the solution to the Dirac equation (where energy depends on and another quantum number ), and by the effect of the magnetic field of the nucleus and quantum electrodynamics effects. The latter induce tiny binding energy differences especially for s electrons that go nearer the nucleus, since these feel a very slightly different nuclear charge, even in one-electron atoms; see Lamb shift.
In atoms with multiple electrons, the energy of an electron depends not only on its orbital, but also on its interactions with other electrons. These interactions depend on the detail of its spatial probability distribution, and so the energy levels of orbitals depend not only on but also on . Higher values of are associated with higher values of energy; for instance, the 2p state is higher than the 2s state. When , the increase in energy of the orbital becomes so large as to push the energy of orbital above the energy of the s orbital in the next higher shell; when the energy is pushed into the shell two steps higher. The filling of the 3d orbitals does not occur until the 4s orbitals have been filled.
The increase in energy for subshells of increasing angular momentum in larger atoms is due to electron–electron interaction effects, and it is specifically related to the ability of low angular momentum electrons to penetrate more effectively toward the nucleus, where they are subject to less screening from the charge of intervening electrons. Thus, in atoms with higher atomic number, the of electrons becomes more and more of a determining factor in their energy, and the principal quantum numbers of electrons becomes less and less important in their energy placement.
The energy sequence of the first 35 subshells (e.g., 1s, 2p, 3d, etc.) is given in the following table. Each cell represents a subshell with and given by its row and column indices, respectively. The number in the cell is the subshell's position in the sequence. For a linear listing of the subshells in terms of increasing energies in multielectron atoms, see the section below.
s p d f g h 1 1 2 2 3 3 4 5 7 4 6 8 10 13 5 9 11 14 17 21 612 15 18 22 26 31 716 19 23 27 32 37 820 24 28 33 38 44 925 29 34 39 45 51 1030 35 40 46 52 59
Note: empty cells indicate non-existent sublevels, while numbers in italics indicate sublevels that could (potentially) exist, but which do not hold electrons in any element currently known. |
Atomic orbital | Electron placement and the periodic table | Electron placement and the periodic table
right|thumb|upright=1.6|Electron atomic and molecular orbitals. The chart of orbitals (left) is arranged by increasing energy (see Madelung rule). Atomic orbits are functions of three variables (two angles, and the distance from the nucleus). These images are faithful to the angular component of the orbital, but not entirely representative of the orbital as a whole.
thumb|Atomic orbitals and periodic table construction
Several rules govern the placement of electrons in orbitals (electron configuration). The first dictates that no two electrons in an atom may have the same set of values of quantum numbers (this is the Pauli exclusion principle). These quantum numbers include the three that define orbitals, as well as the spin magnetic quantum number . Thus, two electrons may occupy a single orbital, so long as they have different values of . Because takes one of only two values ( or −), at most two electrons can occupy each orbital.
Additionally, an electron always tends to fall to the lowest possible energy state. It is possible for it to occupy any orbital so long as it does not violate the Pauli exclusion principle, but if lower-energy orbitals are available, this condition is unstable. The electron will eventually lose energy (by releasing a photon) and drop into the lower orbital. Thus, electrons fill orbitals in the order specified by the energy sequence given above.
This behavior is responsible for the structure of the periodic table. The table may be divided into several rows (called 'periods'), numbered starting with 1 at the top. The presently known elements occupy seven periods. If a certain period has number i, it consists of elements whose outermost electrons fall in the ith shell. Niels Bohr was the first to propose (1923) that the periodicity in the properties of the elements might be explained by the periodic filling of the electron energy levels, resulting in the electronic structure of the atom.
The periodic table may also be divided into several numbered rectangular 'blocks'. The elements belonging to a given block have this common feature: their highest-energy electrons all belong to the same -state (but the associated with that -state depends upon the period). For instance, the leftmost two columns constitute the 's-block'. The outermost electrons of Li and Be respectively belong to the 2s subshell, and those of Na and Mg to the 3s subshell.
The following is the order for filling the "subshell" orbitals, which also gives the order of the "blocks" in the periodic table:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p
The "periodic" nature of the filling of orbitals, as well as emergence of the s, p, d, and f "blocks", is more obvious if this order of filling is given in matrix form, with increasing principal quantum numbers starting the new rows ("periods") in the matrix. Then, each subshell (composed of the first two quantum numbers) is repeated as many times as required for each pair of electrons it may contain. The result is a compressed periodic table, with each entry representing two successive elements:
1s 2s 2p2p2p3s 3p3p3p4s 3d3d3d3d3d4p4p4p5s 4d4d4d4d4d5p5p5p6s4f4f4f4f4f4f4f5d5d5d5d5d6p6p6p7s5f5f5f5f5f5f5f6d6d6d6d6d7p7p7p
Although this is the general order of orbital filling according to the Madelung rule, there are exceptions, and the actual electronic energies of each element are also dependent upon additional details of the atoms (see ).
The number of electrons in an electrically neutral atom increases with the atomic number. The electrons in the outermost shell, or valence electrons, tend to be responsible for an element's chemical behavior. Elements that contain the same number of valence electrons can be grouped together and display similar chemical properties. |
Atomic orbital | Relativistic effects | Relativistic effects
For elements with high atomic number , the effects of relativity become more pronounced, and especially so for s electrons, which move at relativistic velocities as they penetrate the screening electrons near the core of high- atoms. This relativistic increase in momentum for high speed electrons causes a corresponding decrease in wavelength and contraction of 6s orbitals relative to 5d orbitals (by comparison to corresponding s and d electrons in lighter elements in the same column of the periodic table); this results in 6s valence electrons becoming lowered in energy.
Examples of significant physical outcomes of this effect include the lowered melting temperature of mercury (which results from 6s electrons not being available for metal bonding) and the golden color of gold and caesium.
In the Bohr model, an electron has a velocity given by , where is the atomic number, is the fine-structure constant, and is the speed of light. In non-relativistic quantum mechanics, therefore, any atom with an atomic number greater than 137 would require its 1s electrons to be traveling faster than the speed of light. Even in the Dirac equation, which accounts for relativistic effects, the wave function of the electron for atoms with is oscillatory and unbounded. The significance of element 137, also known as untriseptium, was first pointed out by the physicist Richard Feynman. Element 137 is sometimes informally called feynmanium (symbol Fy). However, Feynman's approximation fails to predict the exact critical value of due to the non-point-charge nature of the nucleus and very small orbital radius of inner electrons, resulting in a potential seen by inner electrons which is effectively less than . The critical value, which makes the atom unstable with regard to high-field breakdown of the vacuum and production of electron-positron pairs, does not occur until is about 173. These conditions are not seen except transiently in collisions of very heavy nuclei such as lead or uranium in accelerators, where such electron-positron production from these effects has been claimed to be observed.
There are no nodes in relativistic orbital densities, although individual components of the wave function will have nodes. |
Atomic orbital | pp hybridization (conjectured) | pp hybridization (conjectured)
In late period 8 elements, a hybrid of 8p3/2 and 9p1/2 is expected to exist, where "3/2" and "1/2" refer to the total angular momentum quantum number. This "pp" hybrid may be responsible for the p-block of the period due to properties similar to p subshells in ordinary valence shells. Energy levels of 8p3/2 and 9p1/2 come close due to relativistic spin–orbit effects; the 9s subshell should also participate, as these elements are expected to be analogous to the respective 5p elements indium through xenon. |
Atomic orbital | Transitions between orbitals | Transitions between orbitals
Bound quantum states have discrete energy levels. When applied to atomic orbitals, this means that the energy differences between states are also discrete. A transition between these states (i.e., an electron absorbing or emitting a photon) can thus happen only if the photon has an energy corresponding with the exact energy difference between said states.
Consider two states of the hydrogen atom:
State , , and
State , , and
By quantum theory, state 1 has a fixed energy of , and state 2 has a fixed energy of . Now, what would happen if an electron in state 1 were to move to state 2? For this to happen, the electron would need to gain an energy of exactly . If the electron receives energy that is less than or greater than this value, it cannot jump from state 1 to state 2. Now, suppose we irradiate the atom with a broad-spectrum of light. Photons that reach the atom that have an energy of exactly will be absorbed by the electron in state 1, and that electron will jump to state 2. However, photons that are greater or lower in energy cannot be absorbed by the electron, because the electron can jump only to one of the orbitals, it cannot jump to a state between orbitals. The result is that only photons of a specific frequency will be absorbed by the atom. This creates a line in the spectrum, known as an absorption line, which corresponds to the energy difference between states 1 and 2.
The atomic orbital model thus predicts line spectra, which are observed experimentally. This is one of the main validations of the atomic orbital model.
The atomic orbital model is nevertheless an approximation to the full quantum theory, which only recognizes many electron states. The predictions of line spectra are qualitatively useful but are not quantitatively accurate for atoms and ions other than those containing only one electron. |
Atomic orbital | See also | See also
Atomic electron configuration table
Condensed matter physics
Electron configuration
Energy level
Hund's rules
Molecular orbital
Orbital overlap
Quantum chemistry
Quantum chemistry computer programs
Solid-state physics
Wave function collapse
Wiswesser's rule |
Atomic orbital | References | References
|
Atomic orbital | External links | External links
3D representation of hydrogenic orbitals
The Orbitron, a visualization of all common and uncommon atomic orbitals, from 1s to 7g
Grand table Still images of many orbitals
Category:Atomic physics
Category:Chemical bonding
Category:Electron states
Category:Quantum chemistry
Category:Articles containing video clips |
Atomic orbital | Table of Content | Short description, Electron properties, Formal quantum mechanical definition, Types of orbital, History, Early models, Bohr atom, Modern conceptions and connections to the Heisenberg uncertainty principle, Orbital names, Orbital notation and subshells, X-ray notation, Hydrogen-like orbitals, Quantum numbers, Complex orbitals, Real orbitals, Shapes of orbitals, Orbitals table, Qualitative understanding of shapes, Orbital energy, Electron placement and the periodic table, Relativistic effects, pp hybridization (conjectured), Transitions between orbitals, See also, References, External links |
Amino acid | short description |
class=skin-invert-image|thumb|upright=1.15|Structure of a typical L-alpha-amino acid in the "neutral" form
Amino acids are organic compounds that contain both amino and carboxylic acid functional groups. Although over 500 amino acids exist in nature, by far the most important are the 22 α-amino acids incorporated into proteins. Only these 22 appear in the genetic code of life.
Amino acids can be classified according to the locations of the core structural functional groups (alpha- (α-), beta- (β-), gamma- (γ-) amino acids, etc.); other categories relate to polarity, ionization, and side-chain group type (aliphatic, acyclic, aromatic, polar, etc.). In the form of proteins, amino-acid residues form the second-largest component (water being the largest) of human muscles and other tissues. Beyond their role as residues in proteins, amino acids participate in a number of processes such as neurotransmitter transport and biosynthesis. It is thought that they played a key role in enabling life on Earth and its emergence.
Amino acids are formally named by the IUPAC-IUBMB Joint Commission on Biochemical Nomenclature in terms of the fictitious "neutral" structure shown in the illustration. For example, the systematic name of alanine is 2-aminopropanoic acid, based on the formula . The Commission justified this approach as follows:
The systematic names and formulas given refer to hypothetical forms in which amino groups are unprotonated and carboxyl groups are undissociated. This convention is useful to avoid various nomenclatural problems but should not be taken to imply that these structures represent an appreciable fraction of the amino-acid molecules. |
Amino acid | History | History
The first few amino acids were discovered in the early 1800s. In 1806, French chemists Louis-Nicolas Vauquelin and Pierre Jean Robiquet isolated a compound from asparagus that was subsequently named asparagine, the first amino acid to be discovered. Cystine was discovered in 1810, although its monomer, cysteine, remained undiscovered until 1884. Glycine and leucine were discovered in 1820. The last of the 20 common amino acids to be discovered was threonine in 1935 by William Cumming Rose, who also determined the essential amino acids and established the minimum daily requirements of all amino acids for optimal growth.
The unity of the chemical category was recognized by Wurtz in 1865, but he gave no particular name to it.Menten, P. Dictionnaire de chimie: Une approche étymologique et historique. De Boeck, Bruxelles. link . The first use of the term "amino acid" in the English language dates from 1898, while the German term, , was used earlier. Proteins were found to yield amino acids after enzymatic digestion or acid hydrolysis. In 1902, Emil Fischer and Franz Hofmeister independently proposed that proteins are formed from many amino acids, whereby bonds are formed between the amino group of one amino acid with the carboxyl group of another, resulting in a linear structure that Fischer termed "peptide". |
Amino acid | General structure | General structure
thumb|upright=2.75|The 21 proteinogenic α-amino acids found in eukaryotes, grouped according to their side chains' pKa values and charges carried at physiological pH (7.4)
2-, alpha-, or α-amino acids. have the generic formula in most cases, where R is an organic substituent known as a "side chain".
Of the many hundreds of described amino acids, 22 are proteinogenic ("protein-building"). It is these 22 compounds that combine to give a vast array of peptides and proteins assembled by ribosomes. Non-proteinogenic or modified amino acids may arise from post-translational modification or during nonribosomal peptide synthesis. |
Amino acid | Chirality | Chirality
The carbon atom next to the carboxyl group is called the α–carbon. In proteinogenic amino acids, it bears the amine and the R group or side chain specific to each amino acid, as well as a hydrogen atom. With the exception of glycine, for which the side chain is also a hydrogen atom, the α–carbon is stereogenic. All chiral proteogenic amino acids have the L configuration. They are "left-handed" enantiomers, which refers to the stereoisomers of the alpha carbon.
A few D-amino acids ("right-handed") have been found in nature, e.g., in bacterial envelopes, as a neuromodulator (D-serine), and in some antibiotics. Rarely, D-amino acid residues are found in proteins, and are converted from the L-amino acid as a post-translational modification. |
Amino acid | Side chains | Side chains |
Amino acid | Polar charged side chains | Polar charged side chains
Five amino acids possess a charge at neutral pH. Often these side chains appear at the surfaces on proteins to enable their solubility in water, and side chains with opposite charges form important electrostatic contacts called salt bridges that maintain structures within a single protein or between interfacing proteins. Many proteins bind metal into their structures specifically, and these interactions are commonly mediated by charged side chains such as aspartate, glutamate and histidine. Under certain conditions, each ion-forming group can be charged, forming double salts.
The two negatively charged amino acids at neutral pH are aspartate (Asp, D) and glutamate (Glu, E). The anionic carboxylate groups behave as Brønsted bases in most circumstances. Enzymes in very low pH environments, like the aspartic protease pepsin in mammalian stomachs, may have catalytic aspartate or glutamate residues that act as Brønsted acids.
class=skin-invert-image|thumb|upright=2.05 |Functional groups found in histidine (left), lysine (middle) and arginine (right)
There are three amino acids with side chains that are cations at neutral pH: arginine (Arg, R), lysine (Lys, K) and histidine (His, H). Arginine has a charged guanidino group and lysine a charged alkyl amino group, and are fully protonated at pH 7. Histidine's imidazole group has a pKa of 6.0, and is only around 10% protonated at neutral pH. Because histidine is easily found in its basic and conjugate acid forms it often participates in catalytic proton transfers in enzyme reactions. |
Amino acid | Polar uncharged side chains | Polar uncharged side chains
The polar, uncharged amino acids serine (Ser, S), threonine (Thr, T), asparagine (Asn, N) and glutamine (Gln, Q) readily form hydrogen bonds with water and other amino acids. They do not ionize in normal conditions, a prominent exception being the catalytic serine in serine proteases. This is an example of severe perturbation, and is not characteristic of serine residues in general. Threonine has two chiral centers, not only the L (2S) chiral center at the α-carbon shared by all amino acids apart from achiral glycine, but also (3R) at the β-carbon. The full stereochemical specification is (2S,3R)-L-threonine. |
Amino acid | Hydrophobic side chains | Hydrophobic side chains
Nonpolar amino acid interactions are the primary driving force behind the processes that fold proteins into their functional three dimensional structures. None of these amino acids' side chains ionize easily, and therefore do not have pKas, with the exception of tyrosine (Tyr, Y). The hydroxyl of tyrosine can deprotonate at high pH forming the negatively charged phenolate. Because of this one could place tyrosine into the polar, uncharged amino acid category, but its very low solubility in water matches the characteristics of hydrophobic amino acids well. |
Amino acid | Special case side chains | Special case side chains
Several side chains are not described well by the charged, polar and hydrophobic categories. Glycine (Gly, G) could be considered a polar amino acid since its small size means that its solubility is largely determined by the amino and carboxylate groups. However, the lack of any side chain provides glycine with a unique flexibility among amino acids with large ramifications to protein folding. Cysteine (Cys, C) can also form hydrogen bonds readily, which would place it in the polar amino acid category, though it can often be found in protein structures forming covalent bonds, called disulphide bonds, with other cysteines. These bonds influence the folding and stability of proteins, and are essential in the formation of antibodies. Proline (Pro, P) has an alkyl side chain and could be considered hydrophobic, but because the side chain joins back onto the alpha amino group it becomes particularly inflexible when incorporated into proteins. Similar to glycine this influences protein structure in a way unique among amino acids. Selenocysteine (Sec, U) is a rare amino acid not directly encoded by DNA, but is incorporated into proteins via the ribosome. Selenocysteine has a lower redox potential compared to the similar cysteine, and participates in several unique enzymatic reactions. Pyrrolysine (Pyl, O) is another amino acid not encoded in DNA, but synthesized into protein by ribosomes. It is found in archaeal species where it participates in the catalytic activity of several methyltransferases. |
Amino acid | β- and γ-amino acids | β- and γ-amino acids
Amino acids with the structure , such as β-alanine, a component of carnosine and a few other peptides, are β-amino acids. Ones with the structure are γ-amino acids, and so on, where X and Y are two substituents (one of which is normally H). |
Amino acid | Zwitterions | Zwitterions
class=skin-invert-image|thumb|upright=1.5|Ionization and Brønsted character of N-terminal amino, C-terminal carboxylate, and side chains of amino acid residues
The common natural forms of amino acids have a zwitterionic structure, with ( in the case of proline) and functional groups attached to the same C atom, and are thus α-amino acids, and are the only ones found in proteins during translation in the ribosome.
In aqueous solution at pH close to neutrality, amino acids exist as zwitterions, i.e. as dipolar ions with both and in charged states, so the overall structure is . At physiological pH the so-called "neutral forms" are not present to any measurable degree. Although the two charges in the zwitterion structure add up to zero it is misleading to call a species with a net charge of zero "uncharged".
In strongly acidic conditions (pH below 3), the carboxylate group becomes protonated and the structure becomes an ammonio carboxylic acid, . This is relevant for enzymes like pepsin that are active in acidic environments such as the mammalian stomach and lysosomes, but does not significantly apply to intracellular enzymes. In highly basic conditions (pH greater than 10, not normally seen in physiological conditions), the ammonio group is deprotonated to give .
Although various definitions of acids and bases are used in chemistry, the only one that is useful for chemistry in aqueous solution is that of Brønsted: an acid is a species that can donate a proton to another species, and a base is one that can accept a proton. This criterion is used to label the groups in the above illustration. The carboxylate side chains of aspartate and glutamate residues are the principal Brønsted bases in proteins. Likewise, lysine, tyrosine and cysteine will typically act as a Brønsted acid. Histidine under these conditions can act both as a Brønsted acid and a base. |
Amino acid | Isoelectric point | Isoelectric point
class=skin-invert-image|thumb|right|upright=1.5|Composite of titration curves of twenty proteinogenic amino acids grouped by side chain category
For amino acids with uncharged side-chains the zwitterion predominates at pH values between the two pKa values, but coexists in equilibrium with small amounts of net negative and net positive ions. At the midpoint between the two pKa values, the trace amount of net negative and trace of net positive ions balance, so that average net charge of all forms present is zero. This pH is known as the isoelectric point pI, so pI = (pKa1 + pKa2).
For amino acids with charged side chains, the pKa of the side chain is involved. Thus for aspartate or glutamate with negative side chains, the terminal amino group is essentially entirely in the charged form , but this positive charge needs to be balanced by the state with just one C-terminal carboxylate group is negatively charged. This occurs halfway between the two carboxylate pKa values: pI = (pKa1 + pKa(R)), where pKa(R) is the side chain pKa.
Similar considerations apply to other amino acids with ionizable side-chains, including not only glutamate (similar to aspartate), but also cysteine, histidine, lysine, tyrosine and arginine with positive side chains.
Amino acids have zero mobility in electrophoresis at their isoelectric point, although this behaviour is more usually exploited for peptides and proteins than single amino acids. Zwitterions have minimum solubility at their isoelectric point, and some amino acids (in particular, with nonpolar side chains) can be isolated by precipitation from water by adjusting the pH to the required isoelectric point. |
Amino acid | Physicochemical properties | Physicochemical properties
The 20 canonical amino acids can be classified according to their properties. Important factors are charge, hydrophilicity or hydrophobicity, size, and functional groups. These properties influence protein structure and protein–protein interactions. The water-soluble proteins tend to have their hydrophobic residues (Leu, Ile, Val, Phe, and Trp) buried in the middle of the protein, whereas hydrophilic side chains are exposed to the aqueous solvent. (In biochemistry, a residue refers to a specific monomer within the polymeric chain of a polysaccharide, protein or nucleic acid.) The integral membrane proteins tend to have outer rings of exposed hydrophobic amino acids that anchor them in the lipid bilayer. Some peripheral membrane proteins have a patch of hydrophobic amino acids on their surface that sticks to the membrane. In a similar fashion, proteins that have to bind to positively charged molecules have surfaces rich in negatively charged amino acids such as glutamate and aspartate, while proteins binding to negatively charged molecules have surfaces rich in positively charged amino acids like lysine and arginine. For example, lysine and arginine are present in large amounts in the low-complexity regions of nucleic-acid binding proteins. There are various hydrophobicity scales of amino acid residues.
Some amino acids have special properties. Cysteine can form covalent disulfide bonds to other cysteine residues. Proline forms a cycle to the polypeptide backbone, and glycine is more flexible than other amino acids.
Glycine and proline are strongly present within low complexity regions of both eukaryotic and prokaryotic proteins, whereas the opposite is the case with cysteine, phenylalanine, tryptophan, methionine, valine, leucine, isoleucine, which are highly reactive, or complex, or hydrophobic.
Many proteins undergo a range of posttranslational modifications, whereby additional chemical groups are attached to the amino acid residue side chains sometimes producing lipoproteins (that are hydrophobic), or glycoproteins (that are hydrophilic) allowing the protein to attach temporarily to a membrane. For example, a signaling protein can attach and then detach from a cell membrane, because it contains cysteine residues that can have the fatty acid palmitic acid added to them and subsequently removed. |
Amino acid | Table of standard amino acid abbreviations and properties | Table of standard amino acid abbreviations and properties
Although one-letter symbols are included in the table, IUPAC–IUBMB recommend that "Use of the one-letter symbols should be restricted to the comparison of long sequences".
The one-letter notation was chosen by IUPAC-IUB based on the following rules:
Initial letters are used where there is no ambiguity: C cysteine, H histidine, I isoleucine, M methionine, S serine, V valine,
Where arbitrary assignment is needed, the structurally simpler amino acids are given precedence: A Alanine, G glycine, L leucine, P proline, T threonine,
F PHenylalanine and R aRginine are assigned by being phonetically suggestive,
W tryptophan is assigned based on the double ring being visually suggestive to the bulky letter W,
K lysine and Y tyrosine are assigned as alphabetically nearest to their initials L and T (note that U was avoided for its similarity with V, while X was reserved for undetermined or atypical amino acids); for tyrosine the mnemonic tYrosine was also proposed,
D aspartate was assigned arbitrarily, with the proposed mnemonic asparDic acid; E glutamate was assigned in alphabetical sequence being larger by merely one methylene –CH2– group,
N asparagine was assigned arbitrarily, with the proposed mnemonic asparagiNe; Q glutamine was assigned in alphabetical sequence of those still available (note again that O was avoided due to similarity with D), with the proposed mnemonic Qlutamine.
Amino acid 3- and 1-letter symbols Side chain Hydropathy index Molar absorptivity Molecular mass Abundance in proteins (%) Standard genetic coding,IUPAC notation 3 1 Class Chemical polarity Net chargeat pH 7.4 Wavelength,λmax (nm) Coefficient ε(mM−1·cm−1) Alanine Ala A Aliphatic Nonpolar Neutral 1.8 89.094 8.76 GCN Arginine Arg R Fixed cation Basic polar Positive −4.5 174.203 5.78 MGR, CGY Asparagine Asn N Amide Polar Neutral −3.5 132.119 3.93 AAY Aspartate Asp D Anion Brønsted base Negative −3.5 133.104 5.49 GAY Cysteine Cys C Thiol Brønsted acid Neutral 2.5 250 0.3 121.154 1.38 UGY Glutamine Gln Q Amide Polar Neutral −3.5 146.146 3.9 CAR Glutamate Glu E Anion Brønsted base Negative −3.5 147.131 6.32 GAR Glycine Gly G Aliphatic Nonpolar Neutral −0.4 75.067 7.03 GGN Histidine His H Cationic Brønsted acid and base Positive, 10%Neutral, 90% −3.2 211 5.9 155.156 2.26 CAY Isoleucine Ile I Aliphatic Nonpolar Neutral 4.5 131.175 5.49 AUH Leucine Leu L Aliphatic Nonpolar Neutral 3.8 131.175 9.68 YUR, CUY Lysine Lys K Cation Brønsted acid Positive −3.9 146.189 5.19 AAR Methionine Met M Thioether Nonpolar Neutral 1.9 149.208 2.32 AUG Phenylalanine Phe F Aromatic Nonpolar Neutral 2.8 257, 206, 188 0.2, 9.3, 60.0 165.192 3.87 UUY Proline Pro P Cyclic Nonpolar Neutral −1.6 115.132 5.02 CCN Serine Ser S Hydroxylic Polar Neutral −0.8 105.093 7.14 UCN, AGY Threonine Thr T Hydroxylic Polar Neutral −0.7 119.119 5.53 ACN Tryptophan Trp W Aromatic Nonpolar Neutral −0.9 280, 219 5.6, 47.0 204.228 1.25 UGG Tyrosine Tyr Y Aromatic Brønsted acid Neutral −1.3 274, 222, 193 1.4, 8.0, 48.0 181.191 2.91 UAY Valine Val V Aliphatic Nonpolar Neutral 4.2 117.148 6.73 GUN
Two additional amino acids are in some species coded for by codons that are usually interpreted as stop codons:
21st and 22nd amino acids 3-letter 1-letter Molecular mass Selenocysteine Sec U 168.064 Pyrrolysine Pyl O 255.313
In addition to the specific amino acid codes, placeholders are used in cases where chemical or crystallographic analysis of a peptide or protein cannot conclusively determine the identity of a residue. They are also used to summarize conserved protein sequence motifs. The use of single letters to indicate sets of similar residues is similar to the use of abbreviation codes for degenerate bases.
Ambiguous amino acids 3-letter 1-letter Amino acids included Codons included Any / unknown Xaa X All NNN Asparagine or aspartate Asx B D, N RAY Glutamine or glutamate Glx Z E, Q SAR Leucine or isoleucine Xle J I, L YTR, ATH, CTY Hydrophobic Φ V, I, L, F, W, Y, M NTN, TAY, TGG Aromatic Ω F, W, Y, H YWY, TTY, TGG Aliphatic (non-aromatic) Ψ V, I, L, M VTN, TTR Small π P, G, A, S BCN, RGY, GGR Hydrophilic ζ S, T, H, N, Q, E, D, K, R VAN, WCN, CGN, AGY Positively-charged + K, R, H ARR, CRY, CGR Negatively-charged − D, E GAN
Unk is sometimes used instead of Xaa, but is less standard.
Ter or * (from termination) is used in notation for mutations in proteins when a stop codon occurs. It corresponds to no amino acid at all.
In addition, many nonstandard amino acids have a specific code. For example, several peptide drugs, such as Bortezomib and MG132, are artificially synthesized and retain their protecting groups, which have specific codes. Bortezomib is Pyz–Phe–boroLeu, and MG132 is Z–Leu–Leu–Leu–al. To aid in the analysis of protein structure, photo-reactive amino acid analogs are available. These include photoleucine (pLeu) and photomethionine (pMet). |
Amino acid | Occurrence and functions in biochemistry | Occurrence and functions in biochemistry |
Amino acid | Proteinogenic amino acids | Proteinogenic amino acids
Amino acids are the precursors to proteins. They join by condensation reactions to form short polymer chains called peptides or longer chains called either polypeptides or proteins. These chains are linear and unbranched, with each amino acid residue within the chain attached to two neighboring amino acids. In nature, the process of making proteins encoded by RNA genetic material is called translation and involves the step-by-step addition of amino acids to a growing protein chain by a ribozyme that is called a ribosome. The order in which the amino acids are added is read through the genetic code from an mRNA template, which is an RNA derived from one of the organism's genes.
Twenty-two amino acids are naturally incorporated into polypeptides and are called proteinogenic or natural amino acids. Of these, 20 are encoded by the universal genetic code. The remaining 2, selenocysteine and pyrrolysine, are incorporated into proteins by unique synthetic mechanisms. Selenocysteine is incorporated when the mRNA being translated includes a SECIS element, which causes the UGA codon to encode selenocysteine instead of a stop codon. Pyrrolysine is used by some methanogenic archaea in enzymes that they use to produce methane. It is coded for with the codon UAG, which is normally a stop codon in other organisms.
Several independent evolutionary studies have suggested that Gly, Ala, Asp, Val, Ser, Pro, Glu, Leu, Thr may belong to a group of amino acids that constituted the early genetic code, whereas Cys, Met, Tyr, Trp, His, Phe may belong to a group of amino acids that constituted later additions of the genetic code. |
Amino acid | Standard vs nonstandard amino acids | Standard vs nonstandard amino acids
The 20 amino acids that are encoded directly by the codons of the universal genetic code are called standard or canonical amino acids. A modified form of methionine (N-formylmethionine) is often incorporated in place of methionine as the initial amino acid of proteins in bacteria, mitochondria and plastids (including chloroplasts). Other amino acids are called nonstandard or non-canonical. Most of the nonstandard amino acids are also non-proteinogenic (i.e. they cannot be incorporated into proteins during translation), but two of them are proteinogenic, as they can be incorporated translationally into proteins by exploiting information not encoded in the universal genetic code.
The two nonstandard proteinogenic amino acids are selenocysteine (present in many non-eukaryotes as well as most eukaryotes, but not coded directly by DNA) and pyrrolysine (found only in some archaea and at least one bacterium). The incorporation of these nonstandard amino acids is rare. For example, 25 human proteins include selenocysteine in their primary structure, and the structurally characterized enzymes (selenoenzymes) employ selenocysteine as the catalytic moiety in their active sites. Pyrrolysine and selenocysteine are encoded via variant codons. For example, selenocysteine is encoded by stop codon and SECIS element.
N-formylmethionine (which is often the initial amino acid of proteins in bacteria, mitochondria, and chloroplasts) is generally considered as a form of methionine rather than as a separate proteinogenic amino acid. Codon–tRNA combinations not found in nature can also be used to "expand" the genetic code and form novel proteins known as alloproteins incorporating non-proteinogenic amino acids. |
Amino acid | Non-proteinogenic amino acids | Non-proteinogenic amino acids
Aside from the 22 proteinogenic amino acids, many non-proteinogenic amino acids are known. Those either are not found in proteins (for example carnitine, GABA, levothyroxine) or are not produced directly and in isolation by standard cellular machinery. For example, hydroxyproline, is synthesised from proline. Another example is selenomethionine).
Non-proteinogenic amino acids that are found in proteins are formed by post-translational modification. Such modifications can also determine the localization of the protein, e.g., the addition of long hydrophobic groups can cause a protein to bind to a phospholipid membrane. Examples:
the carboxylation of glutamate allows for better binding of calcium cations,
Hydroxyproline, generated by hydroxylation of proline, is a major component of the connective tissue collagen.
Hypusine in the translation initiation factor EIF5A, contains a modification of lysine.
Some non-proteinogenic amino acids are not found in proteins. Examples include 2-aminoisobutyric acid and the neurotransmitter gamma-aminobutyric acid. Non-proteinogenic amino acids often occur as intermediates in the metabolic pathways for standard amino acids – for example, ornithine and citrulline occur in the urea cycle, part of amino acid catabolism (see below). A rare exception to the dominance of α-amino acids in biology is the β-amino acid beta alanine (3-aminopropanoic acid), which is used in plants and microorganisms in the synthesis of pantothenic acid (vitamin B5), a component of coenzyme A. |
Amino acid | In mammalian nutrition | In mammalian nutrition
class=skin-invert-image|thumb|right|upright=1.75 |Share of amino acid in various human diets and the resulting mix of amino acids in human blood serum. Glutamate and glutamine are the most frequent in food at over 10%, while alanine, glutamine, and glycine are the most common in blood.|alt=Diagram showing the relative occurrence of amino acids in blood serum as obtained from diverse diets.
Animals ingest amino acids in the form of protein. The protein is broken down into its constituent amino acids in the process of digestion. The amino acids are then used to synthesize new proteins and other nitrogenous biomolecules, or they are further catabolized through oxidation to provide a source of energy. The oxidation pathway starts with the removal of the amino group by a transaminase; the amino group is then fed into the urea cycle. The other product of transamidation is a keto acid that enters the citric acid cycle. Glucogenic amino acids can also be converted into glucose, through gluconeogenesis.
Of the 20 standard amino acids, nine (His, Ile, Leu, Lys, Met, Phe, Thr, Trp and Val) are called essential amino acids because the human body cannot synthesize them from other compounds at the level needed for normal growth, so they must be obtained from food. |
Amino acid | Semi-essential and conditionally essential amino acids, and juvenile requirements | Semi-essential and conditionally essential amino acids, and juvenile requirements
In addition, cysteine, tyrosine, and arginine are considered semiessential amino acids, and taurine a semi-essential aminosulfonic acid in children. Some amino acids are conditionally essential for certain ages or medical conditions. Essential amino acids may also vary from species to species. The metabolic pathways that synthesize these monomers are not fully developed. |
Amino acid | Non-protein functions | Non-protein functions
Many proteinogenic and non-proteinogenic amino acids have biological functions beyond being precursors to proteins and peptides. In humans, amino acids also have important roles in diverse biosynthetic pathways. Defenses against herbivores in plants sometimes employ amino acids. Examples: |
Amino acid | Standard amino acids | Standard amino acids
Tryptophan is a precursor of the neurotransmitter serotonin.
Tyrosine (and its precursor phenylalanine) are precursors of the catecholamine neurotransmitters dopamine, epinephrine and norepinephrine and various trace amines.
Phenylalanine is a precursor of phenethylamine and tyrosine in humans. In plants, it is a precursor of various phenylpropanoids, which are important in plant metabolism.
Glycine is a precursor of porphyrins such as heme.
Arginine is a precursor of nitric oxide.
Ornithine and S-adenosylmethionine are precursors of polyamines.
Aspartate, glycine, and glutamine are precursors of nucleotides. |
Amino acid | Roles for nonstandard amino acids | Roles for nonstandard amino acids
Carnitine is used in lipid transport.
gamma-aminobutyric acid is a neurotransmitter.
5-HTP (5-hydroxytryptophan) is used for experimental treatment of depression.
L-DOPA (L-dihydroxyphenylalanine) for Parkinson's treatment,
Eflornithine inhibits ornithine decarboxylase and used in the treatment of sleeping sickness.
Canavanine, an analogue of arginine found in many legumes is an antifeedant, protecting the plant from predators.
Mimosine found in some legumes, is another possible antifeedant. This compound is an analogue of tyrosine and can poison animals that graze on these plants.
However, not all of the functions of other abundant nonstandard amino acids are known. |
Amino acid | Uses in industry | Uses in industry |
Amino acid | Animal feed | Animal feed
Amino acids are sometimes added to animal feed because some of the components of these feeds, such as soybeans, have low levels of some of the essential amino acids, especially of lysine, methionine, threonine, and tryptophan. Likewise amino acids are used to chelate metal cations in order to improve the absorption of minerals from feed supplements. |
Amino acid | Food | Food
The food industry is a major consumer of amino acids, especially glutamic acid, which is used as a flavor enhancer, and aspartame (aspartylphenylalanine 1-methyl ester), which is used as an artificial sweetener. Amino acids are sometimes added to food by manufacturers to alleviate symptoms of mineral deficiencies, such as anemia, by improving mineral absorption and reducing negative side effects from inorganic mineral supplementation. |
Amino acid | Chemical building blocks | Chemical building blocks
Amino acids are low-cost feedstocks used in chiral pool synthesis as enantiomerically pure building blocks.
Amino acids are used in the synthesis of some cosmetics. |
Amino acid | Aspirational uses | Aspirational uses |
Amino acid | Fertilizer | Fertilizer
The chelating ability of amino acids is sometimes used in fertilizers to facilitate the delivery of minerals to plants in order to correct mineral deficiencies, such as iron chlorosis. These fertilizers are also used to prevent deficiencies from occurring and to improve the overall health of the plants. |
Amino acid | Biodegradable plastics | Biodegradable plastics
Amino acids have been considered as components of biodegradable polymers, which have applications as environmentally friendly packaging and in medicine in drug delivery and the construction of prosthetic implants. An interesting example of such materials is polyaspartate, a water-soluble biodegradable polymer that may have applications in disposable diapers and agriculture. Due to its solubility and ability to chelate metal ions, polyaspartate is also being used as a biodegradable antiscaling agent and a corrosion inhibitor. |
Amino acid | Synthesis | Synthesis |
Amino acid | Chemical synthesis | Chemical synthesis
The commercial production of amino acids usually relies on mutant bacteria that overproduce individual amino acids using glucose as a carbon source. Some amino acids are produced by enzymatic conversions of synthetic intermediates. 2-Aminothiazoline-4-carboxylic acid is an intermediate in one industrial synthesis of L-cysteine for example. Aspartic acid is produced by the addition of ammonia to fumarate using a lyase. |
Amino acid | Biosynthesis | Biosynthesis
In plants, nitrogen is first assimilated into organic compounds in the form of glutamate, formed from alpha-ketoglutarate and ammonia in the mitochondrion. For other amino acids, plants use transaminases to move the amino group from glutamate to another alpha-keto acid. For example, aspartate aminotransferase converts glutamate and oxaloacetate to alpha-ketoglutarate and aspartate. Other organisms use transaminases for amino acid synthesis, too.
Nonstandard amino acids are usually formed through modifications to standard amino acids. For example, homocysteine is formed through the transsulfuration pathway or by the demethylation of methionine via the intermediate metabolite S-adenosylmethionine, while hydroxyproline is made by a post translational modification of proline.
Microorganisms and plants synthesize many uncommon amino acids. For example, some microbes make 2-aminoisobutyric acid and lanthionine, which is a sulfide-bridged derivative of alanine. Both of these amino acids are found in peptidic lantibiotics such as alamethicin. However, in plants, 1-aminocyclopropane-1-carboxylic acid is a small disubstituted cyclic amino acid that is an intermediate in the production of the plant hormone ethylene. |
Amino acid | Primordial synthesis | Primordial synthesis
The formation of amino acids and peptides is assumed to have preceded and perhaps induced the emergence of life on earth. Amino acids can form from simple precursors under various conditions. Surface-based chemical metabolism of amino acids and very small compounds may have led to the build-up of amino acids, coenzymes and phosphate-based small carbon molecules. Amino acids and similar building blocks could have been elaborated into proto-peptides, with peptides being considered key players in the origin of life.
class=skin-invert-image|thumb|upright=1.75 |right|The Strecker amino acid synthesis|alt=For the steps in the reaction, see the text.
In the famous Urey-Miller experiment, the passage of an electric arc through a mixture of methane, hydrogen, and ammonia produces a large number of amino acids. Since then, scientists have discovered a range of ways and components by which the potentially prebiotic formation and chemical evolution of peptides may have occurred, such as condensing agents, the design of self-replicating peptides and a number of non-enzymatic mechanisms by which amino acids could have emerged and elaborated into peptides. Several hypotheses invoke the Strecker synthesis whereby hydrogen cyanide, simple aldehydes, ammonia, and water produce amino acids.
According to a review, amino acids, and even peptides, "turn up fairly regularly in the various experimental broths that have been allowed to be cooked from simple chemicals. This is because nucleotides are far more difficult to synthesize chemically than amino acids." For a chronological order, it suggests that there must have been a 'protein world' or at least a 'polypeptide world', possibly later followed by the 'RNA world' and the 'DNA world'. Codon–amino acids mappings may be the biological information system at the primordial origin of life on Earth. While amino acids and consequently simple peptides must have formed under different experimentally probed geochemical scenarios, the transition from an abiotic world to the first life forms is to a large extent still unresolved. |
Amino acid | Reactions | Reactions
Amino acids undergo the reactions expected of the constituent functional groups. |
Amino acid | Peptide bond formation | Peptide bond formation
thumbnail|right|upright=1.75 |The condensation of two amino acids to form a dipeptide. The two amino acid residues are linked through a peptide bond.|alt=Two amino acids are shown next to each other. One loses a hydrogen and oxygen from its carboxyl group (COOH) and the other loses a hydrogen from its amino group (NH2). This reaction produces a molecule of water (H2O) and two amino acids joined by a peptide bond (–CO–NH–). The two joined amino acids are called a dipeptide.
As both the amine and carboxylic acid groups of amino acids can react to form amide bonds, one amino acid molecule can react with another and become joined through an amide linkage. This polymerization of amino acids is what creates proteins. This condensation reaction yields the newly formed peptide bond and a molecule of water. In cells, this reaction does not occur directly; instead, the amino acid is first activated by attachment to a transfer RNA molecule through an ester bond. This aminoacyl-tRNA is produced in an ATP-dependent reaction carried out by an aminoacyl tRNA synthetase. This aminoacyl-tRNA is then a substrate for the ribosome, which catalyzes the attack of the amino group of the elongating protein chain on the ester bond. As a result of this mechanism, all proteins made by ribosomes are synthesized starting at their N-terminus and moving toward their C-terminus.
However, not all peptide bonds are formed in this way. In a few cases, peptides are synthesized by specific enzymes. For example, the tripeptide glutathione is an essential part of the defenses of cells against oxidative stress. This peptide is synthesized in two steps from free amino acids. In the first step, gamma-glutamylcysteine synthetase condenses cysteine and glutamate through a peptide bond formed between the side chain carboxyl of the glutamate (the gamma carbon of this side chain) and the amino group of the cysteine. This dipeptide is then condensed with glycine by glutathione synthetase to form glutathione.
In chemistry, peptides are synthesized by a variety of reactions. One of the most-used in solid-phase peptide synthesis uses the aromatic oxime derivatives of amino acids as activated units. These are added in sequence onto the growing peptide chain, which is attached to a solid resin support. Libraries of peptides are used in drug discovery through high-throughput screening.
The combination of functional groups allow amino acids to be effective polydentate ligands for metal–amino acid chelates.
The multiple side chains of amino acids can also undergo chemical reactions. |
Amino acid | Catabolism | Catabolism
class=skin-invert-image|thumb|upright=1.75 |Catabolism of proteinogenic amino acids. Amino acids can be classified according to the properties of their main degradation products:
* Glucogenic, with the products having the ability to form glucose by gluconeogenesis
* Ketogenic, with the products not having the ability to form glucose. These products may still be used for ketogenesis or lipid synthesis.
* Amino acids catabolized into both glucogenic and ketogenic products.
Degradation of an amino acid often involves deamination by moving its amino group to α-ketoglutarate, forming glutamate. This process involves transaminases, often the same as those used in amination during synthesis. In many vertebrates, the amino group is then removed through the urea cycle and is excreted in the form of urea. However, amino acid degradation can produce uric acid or ammonia instead. For example, serine dehydratase converts serine to pyruvate and ammonia. After removal of one or more amino groups, the remainder of the molecule can sometimes be used to synthesize new amino acids, or it can be used for energy by entering glycolysis or the citric acid cycle, as detailed in image at right. |
Amino acid | Complexation | Complexation
Amino acids are bidentate ligands, forming transition metal amino acid complexes.
class=skin-invert-image|420px |
Amino acid | Chemical analysis | Chemical analysis
The total nitrogen content of organic matter is mainly formed by the amino groups in proteins. The Total Kjeldahl Nitrogen (TKN) is a measure of nitrogen widely used in the analysis of (waste) water, soil, food, feed and organic matter in general. As the name suggests, the Kjeldahl method is applied. More sensitive methods are available. |
Amino acid | See also | See also
Amino acid dating
Beta-peptide
Degron
Erepsin
Homochirality
Hyperaminoacidemia
Leucines
Miller–Urey experiment
Nucleic acid sequence
RNA codon table |
Amino acid | Notes | Notes |
Amino acid | References | References |
Amino acid | Further reading | Further reading
|
Amino acid | External links | External links
Category:Nitrogen cycle
Category:Zwitterions |
Amino acid | Table of Content | short description, History, General structure, Chirality, Side chains, Polar charged side chains, Polar uncharged side chains, Hydrophobic side chains, Special case side chains, β- and γ-amino acids, Zwitterions, Isoelectric point, Physicochemical properties, Table of standard amino acid abbreviations and properties, Occurrence and functions in biochemistry, Proteinogenic amino acids, Standard vs nonstandard amino acids, Non-proteinogenic amino acids, In mammalian nutrition, Semi-essential and conditionally essential amino acids, and juvenile requirements, Non-protein functions, Standard amino acids, Roles for nonstandard amino acids, Uses in industry, Animal feed, Food, Chemical building blocks, Aspirational uses, Fertilizer, Biodegradable plastics, Synthesis, Chemical synthesis, Biosynthesis, Primordial synthesis, Reactions, Peptide bond formation, Catabolism, Complexation, Chemical analysis, See also, Notes, References, Further reading, External links |
Alan Turing | Short description | Alan Mathison Turing (; 23 June 1912 – 7 June 1954) was an English mathematician, computer scientist, logician, cryptanalyst, philosopher and theoretical biologist. He was highly influential in the development of theoretical computer science, providing a formalisation of the concepts of algorithm and computation with the Turing machine, which can be considered a model of a general-purpose computer. Turing is widely considered to be the father of theoretical computer science.
Born in London, Turing was raised in southern England. He graduated from King's College, Cambridge, and in 1938, earned a doctorate degree from Princeton University. During World War II, Turing worked for the Government Code and Cypher School at Bletchley Park, Britain's codebreaking centre that produced Ultra intelligence. He led Hut 8, the section responsible for German naval cryptanalysis. Turing devised techniques for speeding the breaking of German ciphers, including improvements to the pre-war Polish bomba method, an electromechanical machine that could find settings for the Enigma machine. He played a crucial role in cracking intercepted messages that enabled the Allies to defeat the Axis powers in many engagements, including the Battle of the Atlantic.A number of sources state that Winston Churchill said that Turing made the single biggest contribution to Allied victory in the war against Nazi Germany. Whilst it may be a defensible claim, both the Churchill Centre and Turing's biographer Andrew Hodges have stated they know of no documentary evidence to support it, nor the date or context in which Churchill supposedly made it, and the Churchill Centre lists it among their Churchill 'Myths', see and A BBC News profile piece that repeated the Churchill claim has subsequently been amended to say there is no evidence for it. See Official war historian Harry Hinsley estimated that this work shortened the war in Europe by more than two years but added the caveat that this did not account for the use of the atomic bomb and other eventualities. Transcript of a lecture given on Tuesday 19 October 1993 at Cambridge University
After the war, Turing worked at the National Physical Laboratory, where he designed the Automatic Computing Engine, one of the first designs for a stored-program computer. In 1948, Turing joined Max Newman's Computing Machine Laboratory at the University of Manchester, where he contributed to the development of early Manchester computers and became interested in mathematical biology. Turing wrote on the chemical basis of morphogenesis and predicted oscillating chemical reactions such as the Belousov–Zhabotinsky reaction, first observed in the 1960s. Despite these accomplishments, he was never fully recognised during his lifetime because much of his work was covered by the Official Secrets Act.
In 1952, Turing was prosecuted for homosexual acts. He accepted hormone treatment, a procedure commonly referred to as chemical castration, as an alternative to prison. Turing died on 7 June 1954, aged 41, from cyanide poisoning. An inquest determined his death as suicide, but the evidence is also consistent with accidental poisoning.
Following a campaign in 2009, British prime minister Gordon Brown made an official public apology for "the appalling way [Turing] was treated". Queen Elizabeth II granted a pardon in 2013. The term "Alan Turing law" is used informally to refer to a 2017 law in the UK that retroactively pardoned men cautioned or convicted under historical legislation that outlawed homosexual acts.
Turing left an extensive legacy in mathematics and computing which has become widely recognised with statues and many things named after him, including an annual award for computing innovation. His portrait appears on the Bank of England £50 note, first released on 23 June 2021 to coincide with his birthday. The audience vote in a 2019 BBC series named Turing the greatest person of the 20th century. |
Alan Turing | Early life and education | Early life and education |
Alan Turing | Family | Family
thumb|right|upright|English Heritage blue plaque in Maida Vale, London marking Turing's birthplace in 1912
Turing was born in Maida Vale, London, while his father, Julius Mathison Turing, was on leave from his position with the Indian Civil Service (ICS) of the British Raj government at Chatrapur, then in the Madras Presidency and presently in Odisha state, in India. Turing's father was the son of a clergyman, the Rev. John Robert Turing, from a Scottish family of merchants that had been based in the Netherlands and included a baronet. Turing's mother, Julius's wife, was Ethel Sara Turing (), daughter of Edward Waller Stoney, chief engineer of the Madras Railways. The Stoneys were a Protestant Anglo-Irish gentry family from both County Tipperary and County Longford, while Ethel herself had spent much of her childhood in County Clare. Julius and Ethel married on 1 October 1907 at the Church of Ireland St. Bartholomew's Church on Clyde Road in Ballsbridge, Dublin.Irish Marriages 1845–1958 / Dublin South, Dublin, Ireland / Group Registration ID 1990366, SR District/Reg Area, Dublin South
Julius's work with the ICS brought the family to British India, where his grandfather had been a general in the Bengal Army. However, both Julius and Ethel wanted their children to be brought up in Britain, so they moved to Maida Vale, London, where Alan Turing was born on 23 June 1912, as recorded by a blue plaque on the outside of the house of his birth,, later the Colonnade Hotel. Turing had an elder brother, John Ferrier Turing, father of Dermot Turing, 12th Baronet of the Turing baronets.
Turing's father's civil service commission was still active during Turing's childhood years, and his parents travelled between Hastings in the United Kingdom and India, leaving their two sons to stay with a retired Army couple. At Hastings, Turing stayed at Baston Lodge, Upper Maze Hill, St Leonards-on-Sea, now marked with a blue plaque. The plaque was unveiled on 23 June 2012, the centenary of Turing's birth.
Very early in life, Turing's parents purchased a house in Guildford in 1927, and Turing lived there during school holidays. The location is also marked with a blue plaque. |
Alan Turing | School | School
thumb|Turing at age 16,
Turing's parents enrolled him at St Michael's, a primary school at 20 Charles Road, St Leonards-on-Sea, from the age of six to nine. The headmistress recognised his talent, noting that she "...had clever boys and hardworking boys, but Alan is a genius".
Between January 1922 and 1926, Turing was educated at Hazelhurst Preparatory School, an independent school in the village of Frant in Sussex (now East Sussex). In 1926, at the age of 13, he went on to Sherborne School, an independent boarding school in the market town of Sherborne in Dorset, where he boarded at Westcott House. The first day of term coincided with the 1926 General Strike, in Britain, but Turing was so determined to attend that he rode his bicycle unaccompanied from Southampton to Sherborne, stopping overnight at an inn.
Turing's natural inclination towards mathematics and science did not earn him respect from some of the teachers at Sherborne, whose definition of education placed more emphasis on the classics. His headmaster wrote to his parents: "I hope he will not fall between two stools. If he is to stay at public school, he must aim at becoming educated. If he is to be solely a Scientific Specialist, he is wasting his time at a public school". Despite this, Turing continued to show remarkable ability in the studies he loved, solving advanced problems in 1927 without having studied even elementary calculus. In 1928, aged 16, Turing encountered Albert Einstein's work; not only did he grasp it, but it is possible that he managed to deduce Einstein's questioning of Newton's laws of motion from a text in which this was never made explicit. |
Alan Turing | Christopher Morcom | Christopher Morcom
At Sherborne, Turing formed a significant friendship with fellow pupil Christopher Collan Morcom (13 July 1911 – 13 February 1930), who has been described as Turing's first love. Their relationship provided inspiration in Turing's future endeavours, but it was cut short by Morcom's death, in February 1930, from complications of bovine tuberculosis, contracted after drinking infected cow's milk some years previously.
The event caused Turing great sorrow. He coped with his grief by working that much harder on the topics of science and mathematics that he had shared with Morcom. In a letter to Morcom's mother, Frances Isobel Morcom (née Swan), Turing wrote:
Turing's relationship with Morcom's mother continued long after Morcom's death, with her sending gifts to Turing, and him sending letters, typically on Morcom's birthday. A day before the third anniversary of Morcom's death (13 February 1933), he wrote to Mrs. Morcom:
Some have speculated that Morcom's death was the cause of Turing's atheism and materialism. Apparently, at this point in his life he still believed in such concepts as a spirit, independent of the body and surviving death. In a later letter, also written to Morcom's mother, Turing wrote: |
Alan Turing | University and work on computability | University and work on computability
thumb|Turing in the 1930s
After graduating from Sherborne, Turing applied for several Cambridge colleges scholarships, including Trinity and King's, eventually earning an £80 per annum scholarship (equivalent to about £4,300 as of 2023) to study at the latter. There, Turing studied the undergraduate course in Schedule B (Schedule B was a three-year scheme consisting of Parts I and II, of the Mathematical Tripos, with extra courses at the end of the third year, as Part III only emerged as a separate degree in 1934 from February 1931 to November 1934 at King's College, Cambridge, where he was awarded first-class honours in mathematics. His dissertation, On the Gaussian error function, written during his senior year and delivered in November 1934 (with a deadline date of 6 December) proved a version of the central limit theorem. It was finally accepted on 16 March 1935. By spring of that same year, Turing started his master's course (Part III)—which he completed in 1937—and, at the same time, he published his first paper, a one-page article called Equivalence of left and right almost periodicity (sent on 23 April), featured in the tenth volume of the Journal of the London Mathematical Society. Later that year, Turing was elected a Fellow of King's College on the strength of his dissertation where he served as a lecturer. However, and, unknown to Turing, this version of the theorem he proved in his paper, had already been proven, in 1922, by Jarl Waldemar Lindeberg. Despite this, the committee found Turing's methods original and so regarded the work worthy of consideration for the fellowship. Abram Besicovitch's report for the committee went so far as to say that if Turing's work had been published before Lindeberg's, it would have been "an important event in the mathematical literature of that year".
Between the springs of 1935 and 1936, at the same time as Alonzo Church, Turing worked on the decidability of problems, starting from Gödel's incompleteness theorems. In mid-April 1936, Turing sent Max Newman the first draft typescript of his investigations. That same month, Church published his An Unsolvable Problem of Elementary Number Theory, with similar conclusions to Turing's then-yet unpublished work. Finally, on 28 May of that year, he finished and delivered his 36-page paper for publication called "On Computable Numbers, with an Application to the Entscheidungsproblem". It was published in the Proceedings of the London Mathematical Society journal in two parts, the first on 30 November and the second on 23 December. In this paper, Turing reformulated Kurt Gödel's 1931 results on the limits of proof and computation, replacing Gödel's universal arithmetic-based formal language with the formal and simple hypothetical devices that became known as Turing machines. The Entscheidungsproblem (decision problem) was originally posed by German mathematician David Hilbert in 1928. Turing proved that his "universal computing machine" would be capable of performing any conceivable mathematical computation if it were representable as an algorithm. He went on to prove that there was no solution to the decision problem by first showing that the halting problem for Turing machines is undecidable: it is not possible to decide algorithmically whether a Turing machine will ever halt. This paper has been called "easily the most influential math paper in history".
thumb|right|King's College, Cambridge, where Turing was an undergraduate in 1931 and became a Fellow in 1935. The computer room is named after him.
Although Turing's proof was published shortly after Church's equivalent proof using his lambda calculus, Turing's approach is considerably more accessible and intuitive than Church's. It also included a notion of a 'Universal Machine' (now known as a universal Turing machine), with the idea that such a machine could perform the tasks of any other computation machine (as indeed could Church's lambda calculus). According to the Church–Turing thesis, Turing machines and the lambda calculus are capable of computing anything that is computable. John von Neumann acknowledged that the central concept of the modern computer was due to Turing's paper."von Neumann ... firmly emphasised to me, and to others I am sure, that the fundamental conception is owing to Turing—insofar as not anticipated by Babbage, Lovelace and others." Letter by Stanley Frankel to Brian Randell, 1972, quoted in Jack Copeland (2004) The Essential Turing, p. 22. To this day, Turing machines are a central object of study in theory of computation.
From September 1936 to July 1938, Turing spent most of his time studying under Church at Princeton University, in the second year as a Jane Eliza Procter Visiting Fellow. In addition to his purely mathematical work, he studied cryptology and also built three of four stages of an electro-mechanical binary multiplier. In June 1938, he obtained his PhD from the Department of Mathematics at Princeton; his dissertation, Systems of Logic Based on Ordinals, introduced the concept of ordinal logic and the notion of relative computing, in which Turing machines are augmented with so-called oracles, allowing the study of problems that cannot be solved by Turing machines. John von Neumann wanted to hire him as his postdoctoral assistant, but he went back to the United Kingdom.John Von Neumann: The Scientific Genius Who Pioneered the Modern Computer, Game Theory, Nuclear Deterrence, and Much More, Norman MacRae, 1999, American Mathematical Society, Chapter 8 |
Alan Turing | Career and research | Career and research
When Turing returned to Cambridge, he attended lectures given in 1939 by Ludwig Wittgenstein about the foundations of mathematics. The lectures have been reconstructed verbatim, including interjections from Turing and other students, from students' notes. Turing and Wittgenstein argued and disagreed, with Turing defending formalism and Wittgenstein propounding his view that mathematics does not discover any absolute truths, but rather invents them. |
Alan Turing | Cryptanalysis | Cryptanalysis
During the Second World War, Turing was a leading participant in the breaking of German ciphers at Bletchley Park. The historian and wartime codebreaker Asa Briggs has said, "You needed exceptional talent, you needed genius at Bletchley and Turing's was that genius."
From September 1938, Turing worked part-time with the Government Code and Cypher School (GC&CS), the British codebreaking organisation. He concentrated on cryptanalysis of the Enigma cipher machine used by Nazi Germany, together with Dilly Knox, a senior GC&CS codebreaker. Soon after the July 1939 meeting near Warsaw at which the Polish Cipher Bureau gave the British and French details of the wiring of Enigma machine's rotors and their method of decrypting Enigma machine's messages, Turing and Knox developed a broader solution. The Polish method relied on an insecure indicator procedure that the Germans were likely to change, which they in fact did in May 1940. Turing's approach was more general, using crib-based decryption for which he produced the functional specification of the bombe (an improvement on the Polish Bomba).
thumb|right|Two cottages in the stable yard at Bletchley Park. Turing worked here in 1939 and 1940, before moving to Hut 8.
On 4 September 1939, the day after the UK declared war on Germany, Turing reported to Bletchley Park, the wartime station of GC&CS.Copeland, 2006 p. 378. Like all others who came to Bletchley, he was required to sign the Official Secrets Act, in which he agreed not to disclose anything about his work at Bletchley, with severe legal penalties for violating the Act.
Specifying the bombe was the first of five major cryptanalytical advances that Turing made during the war. The others were: deducing the indicator procedure used by the German navy; developing a statistical procedure dubbed Banburismus for making much more efficient use of the bombes; developing a procedure dubbed Turingery for working out the cam settings of the wheels of the Lorenz SZ 40/42 (Tunny) cipher machine and, towards the end of the war, the development of a portable secure voice scrambler at Hanslope Park that was codenamed Delilah.
By using statistical techniques to optimise the trial of different possibilities in the code breaking process, Turing made an innovative contribution to the subject. He wrote two papers discussing mathematical approaches, titled The Applications of Probability to Cryptography and Paper on Statistics of Repetitions, which were of such value to GC&CS and its successor GCHQ that they were not released to the UK National Archives until April 2012, shortly before the centenary of his birth. A GCHQ mathematician, "who identified himself only as Richard," said at the time that the fact that the contents had been restricted under the Official Secrets Act for some 70 years demonstrated their importance, and their relevance to post-war cryptanalysis:
Turing had a reputation for eccentricity at Bletchley Park. He was known to his colleagues as "Prof" and his treatise on Enigma was known as the "Prof's Book". According to historian Ronald Lewin, Jack Good, a cryptanalyst who worked with Turing, said of his colleague:
Peter Hilton recounted his experience working with Turing in Hut 8 in his "Reminiscences of Bletchley Park" from A Century of Mathematics in America:
Hilton echoed similar thoughts in the Nova PBS documentary Decoding Nazi Secrets.
While working at Bletchley, Turing, who was a talented long-distance runner, occasionally ran the to London when he was needed for meetings, and he was capable of world-class marathon standards. Turing tried out for the 1948 British Olympic team, but he was hampered by an injury. His tryout time for the marathon was only 11 minutes slower than British silver medallist Thomas Richards' Olympic race time of 2 hours 35 minutes. He was Walton Athletic Club's best runner, a fact discovered when he passed the group while running alone. When asked why he ran so hard in training he replied:
Due to the problems of counterfactual history, it is hard to estimate the precise effect Ultra intelligence had on the war.See for example and However, official war historian Harry Hinsley estimated that this work shortened the war in Europe by more than two years and saved over 14 million lives. Transcript of a lecture given on Tuesday 19 October 1993 at Cambridge University
At the end of the war, a memo was sent to all those who had worked at Bletchley Park, reminding them that the code of silence dictated by the Official Secrets Act did not end with the war but would continue indefinitely. Thus, even though Turing was appointed an Officer of the Order of the British Empire (OBE) in 1946 by King George VI for his wartime services, his work remained secret for many years. |
Alan Turing | Bombe | Bombe
Within weeks of arriving at Bletchley Park, Turing had specified an electromechanical machine called the bombe, which could break Enigma more effectively than the Polish bomba kryptologiczna, from which its name was derived. The bombe, with an enhancement suggested by mathematician Gordon Welchman, became one of the primary tools, and the major automated one, used to attack Enigma-enciphered messages.
thumbnail|right|A working replica of a bombe now at The National Museum of Computing on Bletchley ParkThe bombe searched for possible correct settings used for an Enigma message (i.e., rotor order, rotor settings and plugboard settings) using a suitable crib: a fragment of probable plaintext. For each possible setting of the rotors (which had on the order of 1019 states, or 1022 states for the four-rotor U-boat variant),Jack Good in "The Men Who Cracked Enigma", 2003: with his caveat: "if my memory is correct". the bombe performed a chain of logical deductions based on the crib, implemented electromechanically.
The bombe detected when a contradiction had occurred and ruled out that setting, moving on to the next. Most of the possible settings would cause contradictions and be discarded, leaving only a few to be investigated in detail. A contradiction would occur when an enciphered letter would be turned back into the same plaintext letter, which was impossible with the Enigma. The first bombe was installed on 18 March 1940. |
Alan Turing | Action This Day | Action This Day
By late 1941, Turing and his fellow cryptanalysts Gordon Welchman, Hugh Alexander and Stuart Milner-Barry were frustrated. Building on the work of the Poles, they had set up a good working system for decrypting Enigma signals, but their limited staff and bombes meant they could not translate all the signals. In the summer, they had considerable success, and shipping losses had fallen to under 100,000 tons a month; however, they badly needed more resources to keep abreast of German adjustments. They had tried to get more people and fund more bombes through the proper channels, but had failed.
On 28 October they wrote directly to Winston Churchill explaining their difficulties, with Turing as the first named. They emphasised how small their need was compared with the vast expenditure of men and money by the forces and compared with the level of assistance they could offer to the forces. As Andrew Hodges, biographer of Turing, later wrote, "This letter had an electric effect." Churchill wrote a memo to General Ismay, which read: "ACTION THIS DAY. Make sure they have all they want on extreme priority and report to me that this has been done." On 18 November, the chief of the secret service reported that every possible measure was being taken. The cryptographers at Bletchley Park did not know of the Prime Minister's response, but as Milner-Barry recalled, "All that we did notice was that almost from that day the rough ways began miraculously to be made smooth."Copeland, The Essential Turing, pp. 336–337 . More than two hundred bombes were in operation by the end of the war. |
Alan Turing | Hut 8 and the naval Enigma | Hut 8 and the naval Enigma
thumb|upright|Statue of Turing holding an Enigma machine by Stephen Kettle at Bletchley Park, commissioned by Sidney Frank, built from half a million pieces of Welsh slate
Turing decided to tackle the particularly difficult problem of cracking the German naval use of Enigma "because no one else was doing anything about it and I could have it to myself". In December 1939, Turing solved the essential part of the naval indicator system, which was more complex than the indicator systems used by the other services.
That same night, he also conceived of the idea of Banburismus, a sequential statistical technique (what Abraham Wald later called sequential analysis) to assist in breaking the naval Enigma, "though I was not sure that it would work in practice, and was not, in fact, sure until some days had actually broken". For this, he invented a measure of weight of evidence that he called the ban. Banburismus could rule out certain sequences of the Enigma rotors, substantially reducing the time needed to test settings on the bombes. Later this sequential process of accumulating sufficient weight of evidence using decibans (one tenth of a ban) was used in cryptanalysis of the Lorenz cipher.
Turing travelled to the United States in November 1942 and worked with US Navy cryptanalysts on the naval Enigma and bombe construction in Washington. He also visited their Computing Machine Laboratory in Dayton, Ohio.
Turing's reaction to the American bombe design was far from enthusiastic:
During this trip, he also assisted at Bell Labs with the development of secure speech devices. He returned to Bletchley Park in March 1943. During his absence, Hugh Alexander had officially assumed the position of head of Hut 8, although Alexander had been de facto head for some time (Turing having little interest in the day-to-day running of the section). Turing became a general consultant for cryptanalysis at Bletchley Park.
Alexander wrote of Turing's contribution: |
Alan Turing | Turingery | Turingery
In July 1942, Turing devised a technique termed Turingery (or jokingly Turingismus) for use against the Lorenz cipher messages produced by the Germans' new Geheimschreiber (secret writer) machine. This was a teleprinter rotor cipher attachment codenamed Tunny at Bletchley Park. Turingery was a method of wheel-breaking, i.e., a procedure for working out the cam settings of Tunny's wheels. He also introduced the Tunny team to Tommy Flowers who, under the guidance of Max Newman, went on to build the Colossus computer, the world's first programmable digital electronic computer, which replaced a simpler prior machine (the Heath Robinson), and whose superior speed allowed the statistical decryption techniques to be applied usefully to the messages. Some have mistakenly said that Turing was a key figure in the design of the Colossus computer. Turingery and the statistical approach of Banburismus undoubtedly fed into the thinking about cryptanalysis of the Lorenz cipher, but he was not directly involved in the Colossus development. |
Alan Turing | Delilah | Delilah
Following his work at Bell Labs in the US, Turing pursued the idea of electronic enciphering of speech in the telephone system. In the latter part of the war, he moved to work for the Secret Service's Radio Security Service (later HMGCC) at Hanslope Park. At the park, he further developed his knowledge of electronics with the assistance of REME officer Donald Bayley. Together they undertook the design and construction of a portable secure voice communications machine codenamed Delilah. The machine was intended for different applications, but it lacked the capability for use with long-distance radio transmissions. In any case, Delilah was completed too late to be used during the war. Though the system worked fully, with Turing demonstrating it to officials by encrypting and decrypting a recording of a Winston Churchill speech, Delilah was not adopted for use. Turing also consulted with Bell Labs on the development of SIGSALY, a secure voice system that was used in the later years of the war. |
Alan Turing | Early computers and the Turing test | Early computers and the Turing test
thumb|Plaque, 78 High Street, Hampton
Between 1945 and 1947, Turing lived in Hampton, London, while he worked on the design of the ACE (Automatic Computing Engine) at the National Physical Laboratory (NPL). He presented a paper on 19 February 1946, which was the first detailed design of a stored-program computer. Von Neumann's incomplete First Draft of a Report on the EDVAC had predated Turing's paper, but it was much less detailed and, according to John R. Womersley, Superintendent of the NPL Mathematics Division, it "contains a number of ideas which are Dr. Turing's own". citing
Although ACE was a feasible design, the effect of the Official Secrets Act surrounding the wartime work at Bletchley Park made it impossible for Turing to explain the basis of his analysis of how a computer installation involving human operators would work. This led to delays in starting the project and he became disillusioned. In late 1947 he returned to Cambridge for a sabbatical year during which he produced a seminal work on Intelligent Machinery that was not published in his lifetime.See While he was at Cambridge, the Pilot ACE was being built in his absence. It executed its first program on 10 May 1950, and a number of later computers around the world owe much to it, including the English Electric DEUCE and the American Bendix G-15. The full version of Turing's ACE was not built until after his death.
According to the memoirs of the German computer pioneer Heinz Billing from the Max Planck Institute for Physics, published by Genscher, Düsseldorf, there was a meeting between Turing and Konrad Zuse. It took place in Göttingen in 1947. The interrogation had the form of a colloquium. Participants were Womersley, Turing, Porter from England and a few German researchers like Zuse, Walther, and Billing (for more details see Herbert Bruderer, Konrad Zuse und die Schweiz).
thumb|right|A blue plaque commmemorating Alan Turing's work at the University of Manchester where he was a Reader from 1948 to 1954
In 1948, Turing was appointed reader in the Mathematics Department at the University of Manchester. He lived at "Copper Folly", 43 Adlington Road, in Wilmslow. A year later, he became deputy director of the Computing Machine Laboratory, where he worked on software for one of the earliest stored-program computers—the Manchester Mark 1. Turing wrote the first version of the Programmer's Manual for this machine, and was recruited by Ferranti as a consultant in the development of their commercialised machine, the Ferranti Mark 1. He continued to be paid consultancy fees by Ferranti until his death. During this time, he continued to do more abstract work in mathematics, and in "Computing Machinery and Intelligence", Turing addressed the problem of artificial intelligence, and proposed an experiment that became known as the Turing test, an attempt to define a standard for a machine to be called "intelligent". The idea was that a computer could be said to "think" if a human interrogator could not tell it apart, through conversation, from a human being. In the paper, Turing suggested that rather than building a program to simulate the adult mind, it would be better to produce a simpler one to simulate a child's mind and then to subject it to a course of education. A reversed form of the Turing test is widely used on the Internet; the CAPTCHA test is intended to determine whether the user is a human or a computer.
In 1948, Turing, working with his former undergraduate colleague, D.G. Champernowne, began writing a chess program for a computer that did not yet exist. By 1950, the program was completed and dubbed the Turochamp. In 1952, he tried to implement it on a Ferranti Mark 1, but lacking enough power, the computer was unable to execute the program. Instead, Turing "ran" the program by flipping through the pages of the algorithm and carrying out its instructions on a chessboard, taking about half an hour per move. The game was recorded. According to Garry Kasparov, Turing's program "played a recognizable game of chess". The program lost to Turing's colleague Alick Glennie, although it is said that it won a game against Champernowne's wife, Isabel.
His Turing test was a significant, characteristically provocative, and lasting contribution to the debate regarding artificial intelligence, which continues after more than half a century. |
Alan Turing | Pattern formation and mathematical biology | Pattern formation and mathematical biology
When Turing was 39 years old in 1951, he turned to mathematical biology, finally publishing his masterpiece "The Chemical Basis of Morphogenesis" in January 1952. He was interested in morphogenesis, the development of patterns and shapes in biological organisms. He suggested that a system of chemicals reacting with each other and diffusing across space, termed a reaction–diffusion system, could account for "the main phenomena of morphogenesis". He used systems of partial differential equations to model catalytic chemical reactions. For example, if a catalyst A is required for a certain chemical reaction to take place, and if the reaction produced more of the catalyst A, then we say that the reaction is autocatalytic, and there is positive feedback that can be modelled by nonlinear differential equations. Turing discovered that patterns could be created if the chemical reaction not only produced catalyst A, but also produced an inhibitor B that slowed down the production of A. If A and B then diffused through the container at different rates, then you could have some regions where A dominated and some where B did. To calculate the extent of this, Turing would have needed a powerful computer, but these were not so freely available in 1951, so he had to use linear approximations to solve the equations by hand. These calculations gave the right qualitative results, and produced, for example, a uniform mixture that oddly enough had regularly spaced fixed red spots. The Russian biochemist Boris Belousov had performed experiments with similar results, but could not get his papers published because of the contemporary prejudice that any such thing violated the second law of thermodynamics. Belousov was not aware of Turing's paper in the Philosophical Transactions of the Royal Society.
Although published before the structure and role of DNA was understood, Turing's work on morphogenesis remains relevant today and is considered a seminal piece of work in mathematical biology. One of the early applications of Turing's paper was the work by James Murray explaining spots and stripes on the fur of cats, large and small. Further research in the area suggests that Turing's work can partially explain the growth of "feathers, hair follicles, the branching pattern of lungs, and even the left-right asymmetry that puts the heart on the left side of the chest". In 2012, Sheth, et al. found that in mice, removal of Hox genes causes an increase in the number of digits without an increase in the overall size of the limb, suggesting that Hox genes control digit formation by tuning the wavelength of a Turing-type mechanism. Later papers were not available until Collected Works of A. M. Turing was published in 1992.
A study conducted in 2023 confirmed Turing's mathematical model hypothesis. Presented by the American Physical Society, the experiment involved growing chia seeds in even layers within trays, later adjusting the available moisture. Researchers experimentally tweaked the factors which appear in the Turing equations, and, as a result, patterns resembling those seen in natural environments emerged. This is believed to be the first time that experiments with living vegetation have verified Turing's mathematical insight. |
Alan Turing | Personal life | Personal life |
Alan Turing | Treasure | Treasure
In the 1940s, Turing became worried about losing his savings in the event of a German invasion. In order to protect it, he bought two silver bars weighing and worth £250 (in 2022, £8,000 adjusted for inflation, £48,000 at spot price) and buried them in a wood near Bletchley Park. Upon returning to dig them up, Turing found that he was unable to break his own code describing where exactly he had hidden them. This, along with the fact that the area had been renovated, meant that he never regained the silver. |
Alan Turing | Engagement | Engagement
In 1941, Turing proposed marriage to Hut 8 colleague Joan Clarke, a fellow mathematician and cryptanalyst, but their engagement was short-lived. After admitting his homosexuality to his fiancée, who was reportedly "unfazed" by the revelation, Turing decided that he could not go through with the marriage. |
Alan Turing | Homosexuality and indecency conviction | Homosexuality and indecency conviction
thumb|left|The Dancehouse Theatre, formerly the Regal Cinema, pictured in 2006, outside of which Turning met Arnold Murray
In December 1951, Turing met Arnold Murray, a 19-year-old unemployed man. Turing was walking along Manchester's Oxford Road when he met Murray just outside the Regal Cinema and invited him to lunch. The two agreed to meet again and in January 1952 began an intimate relationship. On 23 January, Turing's house in Wilmslow was burgled. Murray told Turing that he and the burglar were acquainted, and Turing reported the crime to the police. During the investigation, he acknowledged a sexual relationship with Murray. Homosexual acts were criminal offences in the United Kingdom at that time, and both men were charged with "gross indecency" under Section 11 of the Criminal Law Amendment Act 1885. Initial committal proceedings for the trial were held on 27 February during which Turing's solicitor "reserved his defence", i.e., did not argue or provide evidence against the allegations. The proceedings were held at the Sessions House in Knutsford.
Turing was later convinced by the advice of his brother and his own solicitor, and he entered a plea of guilty. The case, Regina v. Turing and Murray, was brought to trial on 31 March 1952. Turing was convicted and given a choice between imprisonment and probation. His probation would be conditional on his agreement to undergo hormonal physical changes designed to reduce libido, known as "chemical castration". He accepted the option of injections of what was then called stilboestrol (now known as diethylstilbestrol or DES), a synthetic oestrogen; this feminization of his body was continued for the course of one year. The treatment rendered Turing impotent and caused breast tissue to form. In a letter, Turing wrote that "no doubt I shall emerge from it all a different man, but quite who I've not found out". Murray was given a conditional discharge.
Turing's conviction led to the removal of his security clearance and barred him from continuing with his cryptographic consultancy for the Government Communications Headquarters (GCHQ), the British signals intelligence agency that had evolved from GC&CS in 1946, though he kept his academic post. His trial took place only months after the defection to the Soviet Union of Guy Burgess and Donald Maclean, in summer 1951, after which the Foreign Office started to consider anyone known to be homosexual as a potential security risk.
Turing was denied entry into the United States after his conviction in 1952, but was free to visit other European countries. In the summer of 1952 he visited Norway which was more tolerant of homosexuals. Among the various men he met there was one named Kjell Carlson. Kjell intended to visit Turing in the UK but the authorities intercepted Kjell's postcard detailing his travel arrangements and were able to intercept and deport him before the two could meet. It was also during this time that Turing started consulting a psychiatrist, Dr Franz Greenbaum, with whom he got on well and who subsequently became a family friend. |
Alan Turing | Death | Death
thumb|right|A blue plaque on the house at 43 Adlington Road, Wilmslow, where Turing lived and died
On 8 June 1954, at his house at 43 Adlington Road, Wilmslow, Turing's housekeeper found him dead. A post mortem was held that evening, which determined that he had died the previous day at age 41 with cyanide poisoning cited as the cause of death. When his body was discovered, an apple lay half-eaten beside his bed, and although the apple was not tested for cyanide, it was speculated that this was the means by which Turing had consumed a fatal dose.
Turing's brother, John, identified the body the following day and took the advice given by Dr. Greenbaum to accept the verdict of the inquest, as there was little prospect of establishing that the death was accidental. The inquest was held the following day, which determined the cause of death to be suicide. Turing's remains were cremated at Woking Crematorium just two days later on 12 June 1954, with just his mother, brother, and Lyn Newman attending, and his ashes were scattered in the gardens of the crematorium, just as his father's had been. Turing's mother was on holiday in Italy at the time of his death and returned home after the inquest. She never accepted the verdict of suicide.
Philosopher Jack Copeland has questioned various aspects of the coroner's historical verdict. He suggested an alternative explanation for the cause of Turing's death: the accidental inhalation of cyanide fumes from an apparatus used to electroplate gold onto spoons. The potassium cyanide was used to dissolve the gold. Turing had such an apparatus set up in his tiny spare room. Copeland noted that the autopsy findings were more consistent with inhalation than with ingestion of the poison. Turing also habitually ate an apple before going to bed, and it was not unusual for the apple to be discarded half-eaten. Furthermore, Turing had reportedly borne his legal setbacks and hormone treatment (which had been discontinued a year previously) "with good humour" and had shown no sign of despondency before his death. He even set down a list of tasks that he intended to complete upon returning to his office after the holiday weekend. Turing's mother believed that the ingestion was accidental, resulting from her son's careless storage of laboratory chemicals. Turing biographer Andrew Hodges theorised that Turing deliberately made his death look accidental in order to shield his mother from the knowledge that he had killed himself.
Doubts on the suicide thesis have been also cast by John W. Dawson Jr. who, in his review of Hodges' book, recalls "Turing's vulnerable position in the Cold War political climate" and points out that "Turing was found dead by a maid, who discovered him 'lying neatly in his bed'—hardly what one would expect of "a man fighting for life against the suffocation induced by cyanide poisoning." Turing had given no hint of suicidal inclinations to his friends and had made no effort to put his affairs in order.
Hodges and a later biographer, David Leavitt, have both speculated that Turing was re-enacting a scene from the Walt Disney film Snow White and the Seven Dwarfs (1937), his favourite fairy tale. Both men noted that (in Leavitt's words) he took "an especially keen pleasure in the scene where the Wicked Queen immerses her apple in the poisonous brew". and
thumb|Turing's OBE currently held in Sherborne School archives
It has also been suggested that Turing's belief in fortune-telling may have caused his depressed mood. As a youth, Turing had been told by a fortune-teller that he would be a genius. In mid-May 1954, shortly before his death, Turing again decided to consult a fortune-teller during a day-trip to St Annes-on-Sea with the Greenbaum family. According to the Greenbaums' daughter, Barbara: |
Alan Turing | Government apology and pardon | Government apology and pardon
In August 2009, British programmer John Graham-Cumming started a petition urging the British government to apologise for Turing's prosecution as a homosexual. The petition received more than 30,000 signatures.The petition was only open to UK citizens. The prime minister, Gordon Brown, acknowledged the petition, releasing a statement on 10 September 2009 apologising and describing the treatment of Turing as "appalling":
In December 2011, William Jones and his member of Parliament, John Leech, created an e-petition requesting that the British government pardon Turing for his conviction of "gross indecency":
The petition gathered over 37,000 signatures, and was submitted to Parliament by the Manchester MP John Leech but the request was discouraged by Justice Minister Lord McNally, who said:
John Leech, the MP for Manchester Withington (2005–15), submitted several bills to Parliament and led a high-profile campaign to secure the pardon. Leech made the case in the House of Commons that Turing's contribution to the war made him a national hero and that it was "ultimately just embarrassing" that the conviction still stood. Leech continued to take the bill through Parliament and campaigned for several years, gaining the public support of numerous leading scientists, including Stephen Hawking. At the British premiere of a film based on Turing's life, The Imitation Game, the producers thanked Leech for bringing the topic to public attention and securing Turing's pardon. Leech is now regularly described as the "architect" of Turing's pardon and subsequently the Alan Turing Law which went on to secure pardons for 75,000 other men and women convicted of similar crimes.
On 26 July 2012, a bill was introduced in the House of Lords to grant a statutory pardon to Turing for offences under section 11 of the Criminal Law Amendment Act 1885, of which he was convicted on 31 March 1952. Late in the year in a letter to The Daily Telegraph, the physicist Stephen Hawking and 10 other signatories including the Astronomer Royal Lord Rees, President of the Royal Society Sir Paul Nurse, Lady Trumpington (who worked for Turing during the war) and Lord Sharkey (the bill's sponsor) called on Prime Minister David Cameron to act on the pardon request. The government indicated it would support the bill, and it passed its third reading in the House of Lords in October.
At the bill's second reading in the House of Commons on 29 November 2013, Conservative MP Christopher Chope objected to the bill, delaying its passage. The bill was due to return to the House of Commons on 28 February 2014, but before the bill could be debated in the House of Commons, the government elected to proceed under the royal prerogative of mercy. On 24 December 2013, Queen Elizabeth II signed a pardon for Turing's conviction for "gross indecency", with immediate effect. Announcing the pardon, Lord Chancellor Chris Grayling said Turing deserved to be "remembered and recognised for his fantastic contribution to the war effort" and not for his later criminal conviction. The Queen pronounced Turing pardoned in August 2014. It was only the fourth royal pardon granted since the conclusion of the Second World War. Pardons are normally granted only when the person is technically innocent, and a request has been made by the family or other interested party; neither condition was met in regard to Turing's conviction.
In September 2016, the government announced its intention to expand this retroactive exoneration to other men convicted of similar historical indecency offences, in what was described as an "Alan Turing law". The Alan Turing law is now an informal term for the law in the United Kingdom, contained in the Policing and Crime Act 2017, which serves as an amnesty law to retroactively pardon men who were cautioned or convicted under historical legislation that outlawed homosexual acts. The law applies in England and Wales.
On 19 July 2023, following an apology to LGBT veterans from the UK Government, Defence Secretary Ben Wallace suggested Turing should be honoured with a permanent statue on the fourth plinth of Trafalgar Square, describing Turing as "probably the greatest war hero, in my book, of the Second World War, [whose] achievements shortened the war, saved thousands of lives, helped defeat the Nazis. And his story is a sad story of a society and how it treated him." |
Alan Turing | See also | See also
Legacy of Alan Turing
List of things named after Alan Turing |
Alan Turing | References | References |
Alan Turing | Notes | Notes |
Alan Turing | Citations | Citations |
Alan Turing | Works cited | Works cited
in
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Alan Turing | Further reading | Further reading |
Alan Turing | Articles | Articles
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Alan Turing | Books | Books
(originally published in 1983); basis of the film The Imitation Game
Turing's mother, who survived him by many years, wrote this 157-page biography of her son, glorifying his life. It was published in 1959, and so could not cover his war work. Scarcely 300 copies were sold (Sara Turing to Lyn Newman, 1967, Library of St John's College, Cambridge). The six-page foreword by Lyn Irvine includes reminiscences and is more frequently quoted. It was re-published by Cambridge University Press in 2012, to honour the centenary of his birth, and included a new foreword by Martin Davis, as well as a never-before-published memoir by Turing's older brother John F. Turing.
(originally published in 1959 by W. Heffer & Sons, Ltd)
This 1986 Hugh Whitemore play tells the story of Turing's life and death. In the original West End and Broadway runs, Derek Jacobi played Turing and he recreated the role in a 1997 television film based on the play made jointly by the BBC and WGBH, Boston. The play is published by Amber Lane Press, Oxford, ASIN: B000B7TM0Q
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Alan Turing | External links | External links
Oral history interview with Nicholas C. Metropolis, Charles Babbage Institute, University of Minnesota. Metropolis was the first director of computing services at Los Alamos National Laboratory; topics include the relationship between Turing and John von Neumann
How Alan Turing Cracked The Enigma Code Imperial War Museums
Alan Turing Year
CiE 2012: Turing Centenary Conference
Science in the Making Alan Turing's papers in the Royal Society's archives
Alan Turing site maintained by Andrew Hodges including a short biography
AlanTuring.net – Turing Archive for the History of Computing by Jack Copeland
The Turing Digital Archive – contains scans of some unpublished documents and material from the King's College, Cambridge archive
Alan Turing Papers – University of Manchester Library, Manchester
Sherborne School Archives – holds papers relating to Turing's time at Sherborne School
Alan Turing and the ‘Nature of Spirit’ (Old Shirburnian Society)
Alan Turing OBE, PhD, FRS (1912-1954) (Old Shirburnian Society)
Alan Turing plaques recorded on openplaques.org
Alan Turing archive on New Scientist
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Alan Turing | Table of Content | Short description, Early life and education, Family, School, Christopher Morcom, University and work on computability, Career and research, Cryptanalysis, Bombe, Action This Day, Hut 8 and the naval Enigma, Turingery, Delilah, Early computers and the Turing test, Pattern formation and mathematical biology, Personal life, Treasure, Engagement, Homosexuality and indecency conviction, Death, Government apology and pardon, See also, References, Notes, Citations, Works cited, Further reading, Articles, Books, External links |
Area | short description | Area is the measure of a region's size on a surface. The area of a plane region or plane area refers to the area of a shape or planar lamina, while surface area refers to the area of an open surface or the boundary of a three-dimensional object. Area can be understood as the amount of material with a given thickness that would be necessary to fashion a model of the shape, or the amount of paint necessary to cover the surface with a single coat. It is the two-dimensional analogue of the length of a curve (a one-dimensional concept) or the volume of a solid (a three-dimensional concept).
Two different regions may have the same area (as in squaring the circle); by synecdoche, "area" sometimes is used to refer to the region, as in a "polygonal area".
The area of a shape can be measured by comparing the shape to squares of a fixed size. In the International System of Units (SI), the standard unit of area is the square metre (written as m2), which is the area of a square whose sides are one metre long. A shape with an area of three square metres would have the same area as three such squares. In mathematics, the unit square is defined to have area one, and the area of any other shape or surface is a dimensionless real number.
There are several well-known formulas for the areas of simple shapes such as triangles, rectangles, and circles. Using these formulas, the area of any polygon can be found by dividing the polygon into triangles. For shapes with curved boundary, calculus is usually required to compute the area. Indeed, the problem of determining the area of plane figures was a major motivation for the historical development of calculus.
For a solid shape such as a sphere, cone, or cylinder, the area of its boundary surface is called the surface area. Formulas for the surface areas of simple shapes were computed by the ancient Greeks, but computing the surface area of a more complicated shape usually requires multivariable calculus.
Area plays an important role in modern mathematics. In addition to its obvious importance in geometry and calculus, area is related to the definition of determinants in linear algebra, and is a basic property of surfaces in differential geometry.do Carmo, Manfredo (1976). Differential Geometry of Curves and Surfaces. Prentice-Hall. p. 98, In analysis, the area of a subset of the plane is defined using Lebesgue measure,Walter Rudin (1966). Real and Complex Analysis, McGraw-Hill, . though not every subset is measurable if one supposes the axiom of choice.Gerald Folland (1999). Real Analysis: modern techniques and their applications, John Wiley & Sons, Inc., p. 20, In general, area in higher mathematics is seen as a special case of volume for two-dimensional regions.
Area can be defined through the use of axioms, defining it as a function of a collection of certain plane figures to the set of real numbers. It can be proved that such a function exists. |
Area | Formal definition | Formal definition
An approach to defining what is meant by "area" is through axioms. "Area" can be defined as a function from a collection M of a special kinds of plane figures (termed measurable sets) to the set of real numbers, which satisfies the following properties:
For all S in M, .
If S and T are in M then so are and , and also .
If S and T are in M with then is in M and .
If a set S is in M and S is congruent to T then T is also in M and .
Every rectangle R is in M. If the rectangle has length h and breadth k then .
Let Q be a set enclosed between two step regions S and T. A step region is formed from a finite union of adjacent rectangles resting on a common base, i.e. . If there is a unique number c such that for all such step regions S and T, then .
It can be proved that such an area function actually exists. |
Area | Units | Units
thumb|right|alt=A square made of PVC pipe on grass|A square metre quadrat made of PVC pipe
Every unit of length has a corresponding unit of area, namely the area of a square with the given side length. Thus areas can be measured in square metres (m2), square centimetres (cm2), square millimetres (mm2), square kilometres (km2), square feet (ft2), square yards (yd2), square miles (mi2), and so forth. Algebraically, these units can be thought of as the squares of the corresponding length units.
The SI unit of area is the square metre, which is considered an SI derived unit. |