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Title: Generalization of the linearized approximation to the semiclassical initial value representation for reactive flux correlation functions

Abstract

The semiclassical (SC) initial value representation (IVR) provides a general and practical approach for including quantum effects in classical molecular dynamics simulations. The linearized approximation (LA) to the SC-IVR simplifies the description much further, reducing it to the well-known classical Wigner model (i.e., a classical trajectory calculation with a Wigner distribution of initial conditions); the LA is able to describe quantum effects well for short times (t {approx{underscore}lt} {Dirac{underscore}h}{beta}) but not so for longer times. It is shown here how the full SC-IVR approach, which is able to describe quantum effects for long times, can be cast in a form very similar in structure to the LA, with specific application to flux correlation functions relevant to chemical reaction rates. This formulation may thus make it possible to carry out full SC-IVR calculations while still retaining much of the simplifying aspects of its linearized approximation.

Authors:
Publication Date:
Research Org.:
Univ. of California, Berkeley, CA (US); Lawrence Berkeley National Lab., CA (US)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
20013051
DOE Contract Number:  
AC03-76SF00098
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 103; Journal Issue: 47; Other Information: PBD: 25 Nov 1999; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; SEMICLASSICAL APPROXIMATION; MOLECULAR DYNAMICS METHOD; QUANTUM MECHANICS; JACOBIAN FUNCTION

Citation Formats

Miller, W H. Generalization of the linearized approximation to the semiclassical initial value representation for reactive flux correlation functions. United States: N. p., 1999. Web. doi:10.1021/jp9915275.
Miller, W H. Generalization of the linearized approximation to the semiclassical initial value representation for reactive flux correlation functions. United States. https://doi.org/10.1021/jp9915275
Miller, W H. 1999. "Generalization of the linearized approximation to the semiclassical initial value representation for reactive flux correlation functions". United States. https://doi.org/10.1021/jp9915275.
@article{osti_20013051,
title = {Generalization of the linearized approximation to the semiclassical initial value representation for reactive flux correlation functions},
author = {Miller, W H},
abstractNote = {The semiclassical (SC) initial value representation (IVR) provides a general and practical approach for including quantum effects in classical molecular dynamics simulations. The linearized approximation (LA) to the SC-IVR simplifies the description much further, reducing it to the well-known classical Wigner model (i.e., a classical trajectory calculation with a Wigner distribution of initial conditions); the LA is able to describe quantum effects well for short times (t {approx{underscore}lt} {Dirac{underscore}h}{beta}) but not so for longer times. It is shown here how the full SC-IVR approach, which is able to describe quantum effects for long times, can be cast in a form very similar in structure to the LA, with specific application to flux correlation functions relevant to chemical reaction rates. This formulation may thus make it possible to carry out full SC-IVR calculations while still retaining much of the simplifying aspects of its linearized approximation.},
doi = {10.1021/jp9915275},
url = {https://www.osti.gov/biblio/20013051}, journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
issn = {1089-5639},
number = 47,
volume = 103,
place = {United States},
year = {Thu Nov 25 00:00:00 EST 1999},
month = {Thu Nov 25 00:00:00 EST 1999}
}