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9,000
A Simplified Approach to Optimally Controlled Quantum Dynamics
physics.chem-ph
A new formalism for the optimal control of quantum mechanical physical observables is presented. This approach is based on an analogous classical control technique reported previously[J. Botina, H. Rabitz and N. Rahman, J. chem. Phys. Vol. 102, pag. 226 (1995)]. Quantum Lagrange multiplier functions are used to preserv...
physics
9,001
Influence of the Head Group Size on the Direction of Tilt in Langmuir Monolayers
physics.chem-ph
A model of rods with heads of variable size, which are confined to a planar surface, is used to study the influence of the head group size on tilted phases in Langmuir monolayers. Simple free energy considerations as well as exact zero temperature calculations indicate that molecules with small head groups tilt towards...
physics
9,002
Origin of entropy convergence in hydrophobic hydration and protein folding
physics.chem-ph
An information theory model is used to construct a molecular explanation why hydrophobic solvation entropies measured in calorimetry of protein unfolding converge at a common temperature. The entropy convergence follows from the weak temperature dependence of occupancy fluctuations for molecular-scale volumes in water....
physics
9,003
Application of a symmetry-adapted algebraic model to the vibratioinal spectrum of methane
physics.chem-ph
The stretching and bending vibrations of methane are studied in the framework of a symmetry-adapted algebraic model. The model is based on the realization of the one-dimensional Morse potential in terms of a $U(2)$ algebra. For the 44 observed energies we obtain a fit with a r.m.s. deviation of 1.16 cm$^{-1}$ which is ...
physics
9,004
A symmetry-adapted algebraic approach to molecular spectroscopy
physics.chem-ph
We apply a symmetry-adapted algebraic model to the vibrational excitations in D_3h and T_d molecules. A systematic procedure is used to establish the relation between the algebraic and configuration space formulations. In this way we have identified interaction terms that were absent in previous formulations of the vib...
physics
9,005
Optical response of small carbon clusters
physics.chem-ph
We apply the time-dependent local density approximation (TDLDA) to calculate dipole excitations in small carbon clusters. A strong low-frequency mode is found which agrees well with observation for clusters C_n with n in the range 7-15. The size dependence of the mode may be understood simply as the classical resonance...
physics
9,006
A general algebraic model for vibrational molecular spectroscopy
physics.chem-ph
We present a symmetry-adapted version of the vibron model and discuss an application to D_{3h} triatomic molecules: H_3^+, Be_3 and Na_3^+.
physics
9,007
Dimensional perturbation theory for vibration-rotation spectra of linear triatomic molecules
physics.chem-ph
A very efficient large-order perturbation theory is formulated for the nuclear motion of a linear triatomic molecule. To demonstrate the method, all of the experimentally observed rotational energies, with values of $J$ almost up to 100, for the ground and first excited vibrational states of CO$_2$ and for the ground v...
physics
9,008
A collaborative theoretical and experimental study of the structure and electronic excitation spectrum of the BAr and B(Ar)2 complexes
physics.chem-ph
We report the investigation of the 3s <- 2p transition in the BAr2 cluster. In a supersonic expansion of B atoms entrained in Ar, at high beam source backing pressures we observe several features in the fluorescence excitation spectrum which cannot be assigned to the BAr diatom. Using BAr(X, B) potential energy curves ...
physics
9,009
He Scattering from Random Adsorbates, Disordered Compact Islands and Fractal Submonolayers: Intensity Manifestations of Surface Disorder
physics.chem-ph
A theoretical study is made on He scattering from three fundamental classes of disordered ad-layers: (a) Translationally random adsorbates, (b) disordered compact islands and (c) fractal submonolayers. The implications of the results to experimental studies of He scattering from disordered surfaces are discussed, and a...
physics
9,010
Comment on ``Boson-realization model for the vibrational spectra of tetrahedral molecules''
physics.chem-ph
An algebraic model in terms of a local harmonic boson realization was recently proposed to study molecular vibrational spectra [Zhong-Qi Ma et al., Phys. Rev. A 53, 2173 (1996)]. Because of the local nature of the bosons the model has to deal with spurious degrees of freedom. An approach to eliminate the latter from bo...
physics
9,011
A Simple Method for Calculating Quantum Effects on the Temperature Dependence of Bimolecular Reaction Rates: An Application to $CH_4 + H \to CH_3 + H_2$
physics.chem-ph
The temperature dependence of the rate of the reaction CH_4+H \to CH_3+H_2 is studied using classical collision theory with a temperature-dependent effective potential derived from a path integral analysis. Analytical expressions are obtained for the effective potential and for the rate constant. The rate constant expr...
physics
9,012
Transition to the Most Probable Kinetic State in a Pre-Steady State System
physics.chem-ph
A system containing a pre-steady state standard (non-autocatalytic) reaction, with multiple paths, evolves toward a kinetic state with the minimum attainable activation free energy. Displacement of the path frequency distribution in this transition was shown to minimise the affinity linked to this change in activation ...
physics
9,013
A computational study of 13-atom Ne-Ar cluster heat capacities
physics.chem-ph
Heat capacity curves as functions of temperature were calculated using Monte Carlo methods for the series of Ne_(13-n)Ar_n clusters (0 <= n <= 13). The clusters were modeled classically using pairwise additive Lennard-Jones potentials. The J-walking (or jump-walking) method was used to overcome systematic errors due to...
physics
9,014
Some theoretical considerations concerning ion hydration in the case of ion transfer between water and 1,2-dichloroethane
physics.chem-ph
Some aspects of direct ion transfer across the water/1,2-dichloroethane are analyzed using a very simple model based on thermodynamic considerations. It was concluded that ion solvation by water molecules may occur in some particular cases in the organic phase, delivering an important contribution to the Gibbs free ene...
physics
9,015
Molecular Modeling of Trifluoromethanesulfonic Acid for Solvation Theory
physics.chem-ph
Reported here are theoretical calculations on the triflic acid and water, establishing molecular scale information necessary to modeling of the structure, thermodynamics, and ionic transport of Nafion membranes. To characterize side chain flexibility and accessibility of the acid proton, free energies for rotation of b...
physics
9,016
Optimized random phase approximations for arbitrary reference systems: extremum conditions and thermodynamic consistence
physics.chem-ph
The optimized random phase approximation (ORPA) for classical liquids is re-examined in the framework of the generating functional approach to the integral equations. We show that the two main variants of the approximation correspond to the addition of the same correction to two different first order approximations of ...
physics
9,017
Protein structure prediction as a hard optimization problem: the genetic algorithm approach
physics.chem-ph
Protein structure prediction can be shown to be an NP-hard problem; the number of conformations grows exponentially with the number of residues. The native conformations of proteins occupy a very small subset of these, hence an exploratory, robust search algorithm, such as a genetic algorithm (GA), is required. The dyn...
physics
9,018
Decoherent Histories and Non-adiabatic Quantum Molecular Dynamics
physics.chem-ph
The role of quantum coherence loss in mixed quantum-classical dynamical systems is explored in the context of the theory of quantum decoherence introduced recently by Bittner and Rossky. (J. Chem. Phys. {\bf 103}, 8130 (1995)). This theory, which is based upon the consistent histories interpretation of quantum mechanic...
physics
9,019
Numerical Simulations of Free Radical Reactions
physics.chem-ph
We present an overview of the role of quantum coherence in influencing nonadiabatic processes in the condensed phase. Equations of motion for mixed quantum-classical dynamics are derived from the Consistent Histories interpretation of quantum mechanics. Application of the methods toward computing the excited state life...
physics
9,020
A comparison between algebraic models of molecular spectroscopy
physics.chem-ph
We discuss a symmetry-adapted algebraic (or vibron) model for molecular spectroscopy. The model is formulated in terms of tensor operators under the molecular point group. In this way, we have identified interactions that are absent in previous versions of the vibron model, in which the Hamiltonian is expressed in term...
physics
9,021
Adiabatic passage by light-induced potentials in molecules
physics.chem-ph
We present the APLIP process (Adiabatic Passage by Light Induced Potentials) for the adiabatic transfer of a wave packet from one molecular potential to the displaced ground vibrational state of another. The process uses an intermediate state, which is only slightly populated, and a counterintuitive sequence of light p...
physics
9,022
Facilitated alkali ion transfer at the water 1,2-dichloroethane interphase: Ab-initio calculations concerning alkaline metal cation - 1,10-phenanthroline complexes
physics.chem-ph
A series of calculations on the energetics of complexation of alkaline metals with 1,10-phenanthroline are presented. It is an experimental fact that the ordering of the free energy of transfer across the water - 1,2-dichloroethane interphase is governed by the charge / size ratio of the diferent cations; the larger ca...
physics
9,023
Ion Sizes and Finite-Size Corrections for Ionic-Solvation Free Energies
physics.chem-ph
Free energies of ionic solvation calculated from computer simulations exhibit a strong system size dependence. We perform a finite-size analysis based on a dielectric-continuum model with periodic boundary conditions. That analysis results in an estimate of the Born ion size. Remarkably, the finite-size correction appl...
physics
9,024
Hydrogen molecule in a magnetic field: The lowest states of the Pi manifold and the global ground state of the parallel configuration
physics.chem-ph
The electronic structure of the hydrogen molecule in a magnetic field is investigated for parallel internuclear and magnetic field axes. The lowest states of the $\Pi$ manifold are studied for spin singlet and triplet$(M_s = -1) $ as well as gerade and ungerade parity for a broad range of field strengths $0 \leq B \leq...
physics
9,025
The hydrogen molecule in magnetic fields: The ground states of the Sigma manifold of the parallel configuration
physics.chem-ph
The electronic structure of the hydrogen molecule is investigated for the parallel configuration. The ground states of the Sigma manifold are studied for ungerade and gerade parity as well as singlet and triplet states covering a broad regime of field strengths from B = 0 up to B = 100a.u. A variety of interesting phen...
physics
9,026
Semiclassical theory of vibrational energy relaxation
physics.chem-ph
A theory of vibrational energy relaxation based on a semiclassical treatment of the quantum master equation is presented. Using new results on the semiclassical expansion of dipole matrix elements, we show that in the classical limit the master equation reduces to the Zwanzig energy diffusion equation. The leading quan...
physics
9,027
Vibrational Frequencies of the 2p^2A^"_2 and 3d^2E^" States of the Triatomic Deuterium Molecule
physics.chem-ph
We investigated the vibrational energies in the 2p^2A^"_2 and 3d^2E^" states of the triatomic deuterium molecule D_3. The experiments were performed using a fast neutral beam photoionization spectrometer recently developed at Freiburg. A depletion type optical double-resonance scheme using two pulsed dye lasers was app...
physics
9,028
On the interrelation between Gibbs hypotheses and symmetry postulate
physics.chem-ph
The question of the origin of the Gibbs-factorials is reconsidered. It is argued, using the example of the Brownian motion, that their appearance in classical statistical calculations cannot in general be traced back to the symmetry postulate of quantum mechanics as often assumed.
physics
9,029
Algebraic approach to vibrational spectra of tetrahedral molecules: a case study of silicon tetrafluoride
physics.chem-ph
Both the stretch and bend vibrational spectrum and the intensity of infrared transitions in a tetrahedral molecule are studied in a U(2) algebraic model, where the spurious states in the model Hamiltonian and the wavefunctions are exactly removed. As an example, we apply the model to silicon tetrafluoride SiF$_4$.
physics
9,030
U(2) algebraic model applied to stretching vibrational spectra of tetrahedral molecules
physics.chem-ph
The highly excited stretching vibrational energy levels and the intensities of infrared transitions in tetrahedral molecules are studied in a U(2) algebraic model. Its applications to silane and silicon tetrafluoride are presented with smaller standard deviations than those of other models.
physics
9,031
Possible Mechanism of Formation and Stability of Anomalous States of Water
physics.chem-ph
We examine the physical processes which are involved in the formation and stability of the anomalous states of water reported recently. The initial step of adding a small amount of ionic compound XY to pure water leads to the formation of water clusters (X^+)(H2O)_n and (Y^-)(H2O)_n with n>>1. The structure of the clus...
physics
9,032
Ultra-low energy scattering of a He atom off a He dimer
physics.chem-ph
We present a new, mathematically rigorous, method suitable for bound state and scattering processes calculations for various three atomic or molecular systems where the underlying forces are of a hard-core nature. We employed this method to calculate the binding energies and the ultra-low energy scattering phase shifts...
physics
9,033
Overtone spectra and intensities of tetrahedral molecules in boson-realization models
physics.chem-ph
The stretching and bending vibrational spectrum and the intensities of infrared transitions in a tetrahedral molecule are studied in two boson-realization models, where the interactions between stretching and bending vibrations are described by a quadratic cross term and by Fermi resonance terms, called harmonically co...
physics
9,034
Quasi-chemical Theories of Associated Liquids
physics.chem-ph
It is shown how traditional development of theories of fluids based upon the concept of physical clustering can be adapted to an alternative local clustering definition. The alternative definition can preserve a detailed valence description of the interactions between a solution species and its near-neighbors, i.e., co...
physics
9,035
Theory, Simulation and Nanotechnological Applications of Adsorption on a Surface with Defects
physics.chem-ph
Theory of adsorption on a surface with nanolocal defects is proposed. Two efficacy parameters of surface modification for nanotechnological purposes are introduced, where the modification is a creation of nanolocal artificial defects. The first parameter corresponds to applications where it is necessary to increase the...
physics
9,036
Multigrid High Order Mesh Refinement Techniques
physics.chem-ph
A method for performing high order mesh refinement multigrid computations is presented. The Full Approximation Scheme (FAS) multigrid technique is utilized for a sequence of nested patches of increasing resolution. Conservation forms are generated on coarse scales by additional defect correction terms which counter the...
physics
9,037
Experimental Indication of Structural Heterogeneities in Fragile Hydrogen-bonded Liquids
physics.chem-ph
We present the first experimental characterization in molecular fragile glassformers of a 'prepeak that appears significantly below the main peak of the static structure factor. The temperature and density dependences of this prepeak are studied via elastic neutron scattering experiments under high pressure (up to 300 ...
physics
9,038
Effect of Anion Triiodide on the Main Phase Transition of Fully Hydrated Dipalmitoylphosphatidylcholine Bilayers
physics.chem-ph
The paper describes the effect of anion I-3 on thermotropic mesomorphism of fully hydrated dipalmitoylphosphatidylcholine bilayers. The biphasic behaviour of melting temperature - I-3 concentration dependence and the increase of DELTA T values with I-3 concentration (DELTA T = melting temperature - freezing temperature...
physics
9,039
A fully ab initio quartic force field of spectroscopic quality for SO_3
physics.chem-ph
The quartic force field of SO$_3$ was computed fully ab initio using coupled cluster (CCSD(T)) methods and basis sets of up to $spdfgh$ quality. The effect of inner-shell correlation was taken into account. The addition of tight $d$ functions is found to be essential for accurate geometries and harmonic frequencies. Th...
physics
9,040
Ab initio thermochemistry beyond chemical accuracy for first-and second-row compounds
physics.chem-ph
By judicious use of extrapolations to the 1-particle basis set limit and $n$-particle calibration techniques, total atomization energies of molecules with up to four heavy atoms can be obtained with calibration accuracy (1 kJ/mol or better, on average) without any empirical correction. For the SCF energy a 3-point geom...
physics
9,041
Benchmark ab initio thermochemistry of the isomers of diimide, N_2H_2, using accurate computed structures and anharmonic force fields
physics.chem-ph
A benchmark ab initio study on the thermochemistry of the trans-HNNH, cis-HNNH, and H$_2$NN isomers of diazene has been carried out using the CCSD(T) coupled cluster method, basis sets as large as $[7s6p5d4f3g2h/5s4p3d2f1g]$, and extrapolations towards the 1-particle basis set limit. The effects on inner-shell correlat...
physics
9,042
Ab initio calculations with a nonspherical Gaussian basis set: Excited states of the hydrogen molecule
physics.chem-ph
A basis set of generalized nonspherical Gaussian functions (GGTOs) is presented and discussed. As a first example we report on Born-Oppenheimer energies of the hydrogen molecule. Although accurate results have been obtained, we conclude that H_2 is too 'simple' to allow for a substantial gain by using nonspherical func...
physics
9,043
Instantaneous Pair Theory for High-Frequency Vibrational Energy Relaxation in Fluids
physics.chem-ph
Notwithstanding the long and distinguished history of studies of vibrational energy relaxation, exactly how it is that high frequency vibrations manage to relax in a liquid remains somewhat of a mystery. Both experimental and theoretical approaches seem to say that there is a natural frequency range associated with int...
physics
9,044
Application of time-dependent density functional theory to optical activity
physics.chem-ph
As part of a general study of the time-dependent local density approximation (TDLDA), we here report calculations of optical activity of chiral molecules. The theory automatically satisfies sum rules and the Kramers-Kronig relation between circular dichroism and optical rotatory power. We find that the theory describes...
physics
9,045
Coherent nuclear motion in a condensed-phase environment: Wave-packet approach and pump-probe spectroscopy
physics.chem-ph
A quantum-mechanical Gaussian wave-packet approach to the theoretical description of nuclear motions in a condensed-phase environment is developed. General expressions for the time-dependent reduced density matrix are given for a harmonic potential surface, and the exact quantum dynamics is found for a microscopic syst...
physics
9,046
Molecular Realism in Default Models for Information Theories of Hydrophobic Effects
physics.chem-ph
This letter considers several physical arguments about contributions to hydrophobic hydration of inert gases, constructs default models to test them within information theories, and gives information theory predictions using those default models with moment information drawn from simulation of liquid water. Tested phys...
physics
9,047
A definitive heat of vaporization of silicon through benchmark ab initio calculations on SiF_4
physics.chem-ph
In order to resolve a significant uncertainty in the heat of vaporization of silicon -- a fundamental parameter in gas-phase thermochemistry -- $\Delta H^\circ_{f,0}$[Si(g)] has been determined from a thermochemical cycle involving the precisely known experimental heats of formation of SiF_4(g) and F(g) and a benchmark...
physics
9,048
Symplectic algorithm for constant-pressure molecular dynamics using a Nose-Poincare thermostat
physics.chem-ph
We present a new algorithm for isothermal-isobaric molecular-dynamics simulation. The method uses an extended Hamiltonian with an Andersen piston combined with the Nos'e-Poincar'e thermostat, recently developed by Bond, Leimkuhler and Laird [J. Comp. Phys., 151, (1999)]. This Nos'e-Poincar'e-Andersen (NPA) formulation ...
physics
9,049
Fermi resonance-algebraic model for molecular vibrational spectra
physics.chem-ph
A Fermi resonance-algebraic model is proposed for molecular vibrations, where a U(2) algebra is used for describing the vibrations of each bond, and Fermi resonances between stretching and bending modes are taken into account. The model for a bent molecule XY_2 and a molecule XY_3 is successfully applied to fit the rec...
physics
9,050
Algebraic description of anharmonic stretching vibrations
physics.chem-ph
A U(2) algebraic model is presented to describe stretching vibrations of XY$_n$ (n=2, 3, and 4) systems, where anharmonic interactions between the bond modes are considered. This model in a limit corresponds to an anharmonically coupled local mode model. As an example, the model for a molecule XY$_4$ is applied to rece...
physics
9,051
Potential of an ionic impurityin a large $^4$He cluster
physics.chem-ph
This paper presents an analysis of the motion of an impurity ion in a nanometer scale $^4$He cluster. Due to induction forces, ions are strongly localized near the center of the cluster, with a root mean squared thermal displacements of only a few \AA. The trapping potential is found to be nearly harmonic, with a frequ...
physics
9,052
Potential of a neutral impurity in a large $^4$He clusters
physics.chem-ph
This paper presents an analysis of the motion of an neutral impurity species in a nanometer scale $^4$He cluster, extending a previous study of the dynamics of an ionic impurity. It is shown that for realistic neutral impurity-He potentials, such as those of SF$_6$ and OCS, the impurity is kept well away of the the sur...
physics
9,053
On spin-rotation contribution to nuclear spin conversion in C_{3v}-symmetry molecules. Application to CH_3F
physics.chem-ph
The symmetrized contribution of E-type spin-rotation interaction to conversion between spin modifications of E- and A_1-types in molecules with C_{3v}-symmetry is considered. Using the high-J descending of collisional broadening for accidental rotational resonances between these spin modifications, it was possible to c...
physics
9,054
Single and Double Resonance Microwave Spectroscopy in Superfluid $^4$He Clusters
physics.chem-ph
Purely rotational transitions of a molecule, such as HCCCN, embedded in large $^4$He clusters have been detected for the first time. The saturation behavior shows that, in contrast to previous expectations, the microwave line profiles are dominated by inhomogeneous broadening mechanisms. Spectral holes and peaks produc...
physics
9,055
Accurate ab initio anharmonic force field and heat of formation for silane, SiH_4
physics.chem-ph
From large basis set coupled cluster calculations and a minor empirical adjustment, an anharmonic force field for silane has been derived that is consistently of spectroscopic quality ($\pm 1 cm^{-1}$ on vibrational fundamentals) for all isotopomers of silane studied. Inner-shell polarization functions have an apprecia...
physics
9,056
The heat of atomization of sulfur trioxide, SO$_3$ - a benchmark for computational thermochemistry
physics.chem-ph
Calibration ab initio (direct coupled cluster) calculations including basis set extrapolation, relativistic effects, inner-shell correlation, and an anharmonic zero-point energy, predict the total atomization energy at 0 K of SO$_3$ to be 335.96 (observed 335.92$\pm$0.19) kcal/mol. Inner polarization functions make ver...
physics
9,057
Perturbation Theory on Top of Optimized Effective Potential Method
physics.chem-ph
We present a perturbative approach within the scope of Kohn-Sham density functional theory (DFT). The method is based on the exact exchange-only optimized effective potential method, and correlation is included via perturbation expansion using Rayleigh-Schrodinger (RS) perturbation theory (PT). The correlation potentia...
physics
9,058
Orthogonal Linear Combinations of Gaussian Type Orbitals
physics.chem-ph
The set of Gaussian Type Orbitals g(n1,n2,n3) of order (n+1)(n+2)/2, of common n=n1+n2+n3<=7, common center and exponential, is customized to define a set of 2n+1 linear combinations t(n,m) (-n<=m<=n) such that each t(n,m) depends on the azimuthal and polar angle of the spherical coordinate system like the real or imag...
physics
9,059
Light-induced conversion of nuclear spin isomers of molecules
physics.chem-ph
We report on a new phenomenon of molecular nuclear spin isomers conversion in the field of resonant laser radiation. It is based on the isomer-selective optical excitation and the difference of conversion rates for excited and unexcited molecules. We expect the considerable magnitude of the effect for all molecules whi...
physics
9,060
Prototype model for nuclear spin conversion in molecules: The case of "hydrogen"
physics.chem-ph
Using the concept of the so-called quantum relaxation, we build a semiphenomenological model for orto-para conversion of nuclear spin isomers of hydrogen-type molecules.
physics
9,061
Investigation of $^{4}He_{3}$ trimer on the base of Faddeev equations in configuration space
physics.chem-ph
Precise numerical calculations of bound states of a three-atomic Helium cluster are performed. The modern techniques of solution of Faddeev equations are combined to obtain an efficient numerical scheme. Binding energies and other observables for ground and excited states are calculated. Geometric properties of the clu...
physics
9,062
Optimization of Quantum Monte Carlo Wave Functions Using Analytical Energy Derivatives
physics.chem-ph
An algorithm is proposed to optimize quantum Monte Carlo (QMC) wave functions based on New ton's method and analytical computation of the first and second derivatives of the variati onal energy. This direct application of the variational principle yields significantly low er energy than variance minimization methods wh...
physics
9,063
Spin-Lattice Relaxation in Zero-Magnetic Field Indused by Molecular Reorientations
physics.chem-ph
The stochastic Liouville method is used to analyze the general problem of spin-lattice relaxation in zero-field for molecules undergoing Markovian reorientations.
physics
9,064
Spin-Lattice Relaxation in Metal-Organic Platinum(II) Complexes
physics.chem-ph
The dynamics of spin-lattice relaxation (slr) of metal-organic Pt(II) compounds is studied. Often, such systems are characterized by pronounced zero-field splittings (zfs) of the lowest-lying triplets. Previous expressions for the Orbach slr process do not allow to treat such splitting patterns properly. We discuss the...
physics
9,065
Density Functional Study of adsorption of molecular hydrogen on graphene layers
physics.chem-ph
Density functional theory has been used to study the adsorption of molecular H2 on a graphene layer. Different adsorption sites on top of atoms, bonds and the center of carbon hexagons have been considered and compared. We conclude that the most stable configuration of H2 is physisorbed above the center of an hexagon. ...
physics
9,066
Performance of discrete heat engines and heat pumps in finite time
physics.chem-ph
The performance in finite time of a discrete heat engine with internal friction is analyzed. The working fluid of the engine is composed of an ensemble of noninteracting two level systems. External work is applied by changing the external field and thus the internal energy levels. The friction induces a minimal cycle t...
physics
9,067
The Physical-Chemical Mechanism of Water Stream Self-Purification
physics.chem-ph
The self-purification process of water streams is studied and the physical-chemical mechanism of it is determined. The naturally occurring self-purification process at the Boyne River site is monitored. Experiments at several creeks and rivers in GTA area that induced the self-purification process are provided. As a re...
physics
9,068
Ortho-Para Conversion in CH3F. Self-Consistent Theoretical Model
physics.chem-ph
A complete theoretical model of the nuclear spin conversion in 13CH3F induced by intramolecular ortho-para state mixing is proposed. The model contains parameters determined from the level-crossing spectra of the 13CH3F spin conversion. This set of parameters includes the ortho-para decoherence rate, the magnitude of t...
physics
9,069
The Flotational Mechanism of Etobicoke Creek's Self-Purification
physics.chem-ph
A flotational mechanism of Etobicoke Creek's self-purification has been investigated. It is shown that the froth contains a high concentration of polluting agents. Chemical analyses of the top layer of surface water in comparison to both before and after froth collector in the course of a year are provided. As a result...
physics
9,070
Phase changes in 38 atom Lennard-Jones clusters. I: A parallel tempering study in the canonical ensemble
physics.chem-ph
The heat capacity and isomer distributions of the 38 atom Lennard-Jones cluster have been calculated in the canonical ensemble using parallel tempering Monte Carlo methods. A distinct region of temperature is identified that corresponds to equilibrium between the global minimum structure and the icosahedral basin of st...
physics
9,071
Phase changes in 38 atom Lennard-Jones clusters. II: A parallel tempering study of equilibrium and dynamic properties in the molecular dynamics and microcanonical
physics.chem-ph
We study the 38-atom Lennard-Jones cluster with parallel tempering Monte Carlo methods in the microcanonical and molecular dynamics ensembles. A new Monte Carlo algorithm is presented that samples rigorously the molecular dynamics ensemble for a system at constant total energy, linear and angular momenta. By combining ...
physics
9,072
The Induced Self-Purification of Creeks and Rivers
physics.chem-ph
The clean-up of several Creeks and Rivers by induction of a self-purification process was provided. The process took place at all the sites studied with the up to 100% resulted removal of polluting agents depending on the site and nature of the contaminant. The self-purification mechanism could be used for drinking and...
physics
9,073
Thermodynamic Equilibrium in Open Chemical Systems
physics.chem-ph
The article presents new model of equilibrium in open chemical systems suggesting a linear dependence of the reaction shift from equilibrium in presence of the external thermodynamic force. Basic equation of this model contains traditional logarithmic term and a non-traditional parabolic term. At isolated equilibrium t...
physics
9,074
A Hybrid Algebraic/Schrödinger Approach to the 2D Franck-Condon Problem
physics.chem-ph
We use recent results regarding the geometry of the U(3) bosonic algebraic model to motivate a hybrid algebraic-Schr\"odinger approach to the 2D Franck-Condon problem analogous to 1D approaches. This approach allows one to analyze bent to linear Franck-Condon transitions of triatomic molecules as well as clarifies the ...
physics
9,075
Electron-hole pairs multiquantum generation mechanizm in the process of excitation of ZnSCdS-Cu by an atomic hydrogen
physics.chem-ph
The luminecsence of ZnSCdS-Cu phosphors of various CdS consentration (0-40%) is under investigation. The luminescence was exited by hydrogen atoms during adsorbtion of thermal energy during adsorbtion and impact recombination-heterogeneous chemiluminenscence(HCL) are discussed. The monotone lowering of the conductivity...
physics
9,076
Temperature, Pressure & Solvent Dependence of Positronium Acceptor Reactions
physics.chem-ph
Positronium (Ps) reaction rates (k) with weak Acceptors (Ac) leading to the formation of Ps-Ac Complexes show several intriguing features: non-monotonic temperature dependence of k (departing from the usual Arrhenius paradigm), considerable variablity of k with respect to different solvents, and anomalies in response t...
physics
9,077
GRECP/MRD-CI calculations of the spin-orbit splitting in the ground state of Tl and of the spectroscopic properties of TlH
physics.chem-ph
The generalized relativistic effective core potential (GRECP) approach is employed in the framework of multireference single- and double-excitation configuration interaction (MRD-CI) method to calculate the spin-orbit (SO) splitting in the $^2P^o$ ground state of the Tl atom and spectroscopic constants for the $0^+$ gr...
physics
9,078
Rotation in liquid $^4$He: Lessons from a toy model
physics.chem-ph
This paper presents an analysis of a model problem, consisting of two interacting rigid rings, for the rotation of molecules in liquid $^4$He. Due to Bose symmetry, the excitation of the rotor corresponding to a ring of N helium atoms is restricted to states with integer multiples of N quanta of angular momentum. This ...
physics
9,079
Convergence improvement for coupled cluster calculations
physics.chem-ph
Convergence problems in coupled-cluster iterations are discussed, and a new iteration scheme is proposed. Whereas the Jacobi method inverts only the diagonal part of the large matrix of equation coefficients, we invert a matrix which also includes a relatively small number of off-diagonal coefficients, selected accordi...
physics
9,080
Extracting molecular Hamiltonian structure from time-dependent fluorescence intensity data
physics.chem-ph
We propose a formalism for extracting molecular Hamiltonian structure from inversion of time-dependent fluorescence intensity data. The proposed method requires a minimum of \emph{a priori} knowledge about the system and allows for extracting a complete set of information about the Hamiltonian for a pair of molecular e...
physics
9,081
Dynamics of Chemical Reactions: Open Equilibrium
physics.chem-ph
Dynamic properties of chemical reactions and appropriate relationships for open chemical equilibrium are discussed in approach of the chemical dynamics. New way to calculate composition of chemical systems in open equilibrium, based on the amended equation for the change of Gibbs' free energy, was exemplified using rea...
physics
9,082
Spontaneous formation and stability of small GaP fullerenes
physics.chem-ph
We report the spontaneous formation of a GaP fullerene cage in ab-initio Molecular Dynamics simulations starting from a bulk fragment. A systematic study of the geometric and electronic properties of neutral and ionized GaP clusters suggests the stability of hetero-fullerenes formed by a compound with zincblend bulk st...
physics
9,083
Hydration of methanol in water. A DFT-based molecular dynamics study
physics.chem-ph
We studied the hydration of a single methanol molecule in aqueous solution by first-principle DFT-based molecular dynamics simulation. The calculations show that the local structural and short-time dynamical properties of the water molecules remain almost unchanged by the presence of the methanol, confirming the observ...
physics
9,084
The Law of Conservation of Energy in Chemical Reactions
physics.chem-ph
Earlier it has been supposed that the law of conservation of energy in chemical reactions has the following form: DU=DQ-PDV+SUM(muiDN) In the present paper it has been proved by means of the theory of ordinary differential equations that in the biggest part of the chemical reactions it must have the following form: DU=...
physics
9,085
The Heats of Dilution. Calorimetry and Van't-Hoff
physics.chem-ph
Earlier it has been found that there is a big difference between heats of dilution measured by calorimetry and by the Van't-Hoff equation. In the present paper a reason for that is proposed. Experimental data for dilution of benzene and n-hexane in water were used.
physics
9,086
Application of time-dependent density functional theory to electron-vibration coupling in benzene
physics.chem-ph
Optical properties of symmetry-forbidden pi-pi transitions in benzene are calculated with the time-dependent density functional theory (TDDFT), using an adiabatic LDA functional. Quantities calculated are the envelopes of the Franck-Condon factors of the vibrationally promoted transitions and the associated oscillator ...
physics
9,087
Generalized Heitler-London Theory for H_3: A Comparison of the Surface Integral Method with Perturbation Theory
physics.chem-ph
The generalized Heitler-London (GHL) theory provides a straightforward way to express the potential energy surface of H_3 in terms of Coulomb and exchange energies which can be calculated either by perturbation theory or using the surface integral method (SIM). By applying the Rayleigh-Schroedinger perturbation theory,...
physics
9,088
An interpolation model for the equation of state in binary systems
physics.chem-ph
The new interpolation model of state of binary mixture is investigated. This model use only two parameters and produce many type of phase diagrams.
physics
9,089
Determination of some solubilization parameters with surfactants of egg-yolk lecithin multilamellar vesicles by static light-scattering measurements
physics.chem-ph
Effective surfactant:phospholipid ratios (i.e. molar ratios in the mixed aggregates, vesicles or micelles) have been determined by static light-scattering for the interaction of egg-yolk lecithin (EYL) multilamellar vesicles (MLV) with Triton X-100 (TX-100), sodium deoxycholate (DOCNa) and cetyltrimethylammonium bromid...
physics
9,090
An approximate cooperativity analysis by DSC of phase transitions of DPPC-DOCNa dispersions
physics.chem-ph
The effect of solute, sodium deoxycholate bile salt (DOCNa), on the cooperativity of ordered-fluid, fosfolipid phase transition has been investigated by determining of the transition widths in multibilayer dispersions of the dipalmitoylphosphatidylcholine (DPPC)-DOCNa mixtures. The DT1/2 values were determined by diffe...
physics
9,091
Determination of apparent activating energy of solubilizing MLV-DPPC and MLV-egg-yolk lecithin with surfactants by rectangular optic diffusimetry
physics.chem-ph
It were determinated the apparent activating energy of dipalmitoylphosphatidylcholine (DPPC) multilamellar liposome (MLV) solubilizing with sodium deoxycholate (DOCNa) by turbidi-metric measurements and the apparent activating energy of egg-yolk lecithin (EYL)- MLV solubilizing with different surfactants (DOCNa, TX-100...
physics
9,092
Kinetics of solubilization with Triton X-100 of egg-yolk lecithin bilayers containing cholesterol
physics.chem-ph
The titration solubilization of multilamellar egg-yolk lecithin liposomes (MLV-EYL) with Triton X-100 was studied by rectangular optical diffusimetric measurements as a function of cholesterol (Chol) concentration. It was determinated the variation of optic percentage diffu-sion (per mmol surfactant), DDif%/mmol TX-100...
physics
9,093
Pseudo-time Schroedinger equation with absorbing potential for quantum scattering calculations
physics.chem-ph
The Schroedinger equation with an energy-dependent complex absorbing potential, associated with a scattering system, can be reduced for a special choice of the energy-dependence to a harmonic inversion problem of a discrete pseudo-time correlation function. An efficient formula for Green's function matrix elements is a...
physics
9,094
GRECP/RCC calculation of the spectroscopic constants for the HgH molecule and its cation
physics.chem-ph
Generalized relativistic effective core potential (GRECP) calculations of spectroscopic constants of the HgH molecule ground and low excited states and the HgH+ cation ground state are carried out, with correlation included by the Fock-space relativistic coupled cluster (RCC) method. Basis set superposition errors (BSS...
physics
9,095
Quasi-chemical Theory for the Statistical Thermodynamics of the Hard Sphere Fluid
physics.chem-ph
We develop a quasi-chemical theory for the study of packing thermodynamics in dense liquids. The situation of hard-core interactions is addressed by considering the binding of solvent molecules to a precisely defined `cavity' in order to assess the probability that the `cavity' is entirely evacuated. The primitive quas...
physics
9,096
Overcharging by macroions: above all, an entropy effect
physics.chem-ph
Model macroion solutions next to a charged wall show interface \textit{true overcharging}, charge reversal and inversion, and layering. Macroion layering is present, even if the wall or the macroparticle are \textit{uncharged} or if the wall and macroions are like-charged. An effective long-range attractive force betwe...
physics
9,097
The Electrochemical Reduction of Hydrogen in the Presence of Bisulfate on Platinum(111)
physics.chem-ph
A new model for the intermediate compound of the hydrogen evolution reaction (HER) is proposed, for the electrochemical reduction of hydrogen in the presence of bisulfate on platinum(111). The formation of this compound, a regular 2 dimensional honeycomb ice lattice, occurs by a first order phase transitions that invol...
physics
9,098
Static NLO susceptibilities: testing approximation schemes against exact results
physics.chem-ph
The reliability of the approximations commonly adopted in the calculation of static optical (hyper)polarizabilities is tested against exact results obtained for an interesting toy-model. The model accounts for the principal features of typical nonlinear organic materials with mobile electrons strongly coupled to molecu...
physics
9,099
Vibronic contributions to resonant NLO responses: two-photon absorption in push-pull chromophores
physics.chem-ph
Two-photon absorption (TPA) spectra of push-pull chromophores are described in terms of a two-state model accounting for electron-vibration coupling. Vibrations have two main effects in TPA spectra. The most obvious one is the appearance of a vibrational structure in the spectrum; in this respect we find large Herzberg...
physics