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The Journal of Chemical Physics

On bimolecular kinetics, the Bloch equation and Wigner path integrals

Frank J. McLafferty

Published Nov 15, 1985• 0 citations
Publisher

Abstract

We continue our study of Wigner path integrals. We first define a Wigner path integral for the kernel of the Wigner–Bloch equation, solve it for the free particle and harmonic oscillator cases, discuss the physical interpretation which is new and then we apply it (along with the path integral representation of the Liouville equation) to obtain a path integral representation in phase space of the quantum transition state theory of Miller. We also obtain an expression involving products of Wigner kernels for the correlation function form of the exact bimolecular rate constant.

DOI
10.1063/1.449717

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We continue our study of Wigner path integrals. We first define a Wigner path integral for the kernel of the Wigner–Bloch equation, solve it for the free particle and harmonic oscillator cases, discuss the physical interpretation which is new and then we apply it (along with the path integral representation of the Liouville equation) to obtain a path integral representation in phase space of the quantum transition state theory of Miller. We also obtain an expression involving products of Wigner kernels for the correlation function form of the exact bimolecular rate constant.
We present the path-integral solutions to the distributions in classical (Gibbs) and quantum (Wigner) statistical mechanics. The kernel of the distributions are derived in two ways - one by time slicing and defining the appropriate short-time interval phase space matrix element and second by making use of the kernel in the path-integral approach to quantum mechanics. We show that the two approaches are perturbatively identical. We also present another computation for the Wigner kernel, which is also the Liouville kernel, for the harmonic oscillator and free particle. These kernels may be used as the starting point in the perturbative expansion of the Wigner kernel for any potential. With the kernel solved, we essentially solve also the distributions in classical and quantum statistical mechanics.
Abstract Quantum effects can affect the shape of the particle kinetic energy distribution function, as the interaction of a particle with its surroundings restricts the volume of configuration space, which, due to the uncertainty relation, results in an increase in the volume of the momentum space, i.e., in a rise in the fraction of particles with higher momenta. Allowing for quantum effects at calculations of the equilibrium rate constants of inelastic processes is important in consideration of such phenomena as the transition of combustion into detonation, flame propagation, vibrational relaxation, and even thermonuclear fusion at high pressure and low temperatures. Quantum effects are also important in treatment of transport properties of the strongly interacting systems of many particles. In this work the new path integral representation of the quantum Wigner function in the phase space has been developed for canonical ensemble. Explicit analytical expression of the Wigner function has been obtained in harmonic approximation. New quantum Monte‐Carlo method for ab initio calculations of the average values of quantum operators, Wigner function, momentum and position distributions and wave functions of the ground state has been developed and tested. Obtained results are in a very good agreement with available analytical results and results of usual path‐integral Monte‐Carlo method. The developed approach allows simulation of thermodynamic and kinetic properties of quantum systems and calculation average values of quantum operators, when the usual path integral Monte Carlo methods in configurational space failed. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
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The new numerical version of the Wigner approach to quantum mechanics for treatment thermodynamic properties of the strongly interacting systems of particles has been developed for extreme conditions, when there are no small physical parameters and analytical approximations used in different kind of perturbation theories can not be applied. The new path integral representation of the quantum Wigner function in the phase space has been developed for canonical ensemble. Explicit analytical expression of the Wigner function has been obtained in linear and harmonic approximations. The new quantum Monte-Carlo method for calculations of average values of arbitrary quantum operators has been proposed. Preliminary calculations of the momentum distribution function of the Coulomb systems of particles have been carried out. Comparison with classical Maxwell-Boltzmann distribution shows the significant influence of quantum effects on the high energy asymptotics ("tails') of the calculated momentum distribution functions, which resulted in appearance of sharp oscillations.
Abstract In Chapter 2, a path integral representation of the quantum operator e-β H in the case of Hamiltonians H of the separable form p2/2m + V(q) has been constructed. Here, the construction is extended to Hamiltonians that are more general functions of phase space variables. This results in integrals over paths in phase space involving the action expressed in terms of the classical Hamiltonian H(p,q). However, it is shown that, in the general case, the path integral is not completely defined, and this reflects the problem that the classical Hamiltonian does not specify completely the quantum Hamiltonian, due to the problem of ordering quantum operators in products. When the Hamiltonian is a quadratic function of the momentum variables, the integral over momenta is Gaussian and can be performed. In the separable example, the path integral of Chapter 2 is recovered. In the case of the charged particle in a magnetic field a more general form is found, which is ambiguous, since a problem of operator ordering arises, and the ambiguity must be fixed. Hamiltonians that are general quadratic functions provide other important examples, which are analysed thoroughly. Such Hamiltonians appear in the quantization of the motion on Riemannian manifolds. There, the problem of ambiguities is even more severe. The problem is illustrated by the analysis of the quantization of the free motion on the sphere SN−1.
Abstract Functional integrals are basic tools to study first quantum mechanics (QM), and quantum field theory (QFT). The path integral formulation of QM is well suited to the study of systems with an arbitrary number of degrees of freedom. It makes a smooth transition between nonrelativistic QM and QFT possible. The Euclidean functional integral also emphasizes the deep connection between QFT and the statistical physics of systems with short-range interactions near a continuous phase transition. The path integral representation of the matrix elements of the quantum statistical operator e-β H for Hamiltonians of the simple separable form p2/2m +V(q) is derived. To the path integral corresponds a functional measure and expectation values called correlation functions, which are generalized moments, and related to quantum observables, after an analytic continuation in time. The path integral corresponding to the Euclidean action of a harmonic oscillator, to which is added a time-dependent external force, is calculated explicitly. The result is used to generate Gaussian correlation functions and also to reduce the evaluation of path integrals to perturbation theory. The path integral also provides a convenient tool to derive semi-classical approximations.