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Title: Anharmonic Corrections to Variational Transition State Theory Calculations of Rate Constants for a Model Activated Reaction in Solution

Abstract

Previous errors in harmonic variational transition state theory calculations of rate constants for a model of an activated reaction in solution are corrected by including anharmonicities in the calculations of bound state energy levels. Harmonic variational transition state theory including multidimensional quantum mechanical corrections for reaction coordinate motion has previously been used to calculate the rate constant for a reaction model corresponding to a single solute coordinate coupled to a harmonic bath. Comparison of these rate constants with accurate quantum mechanical rate constants showed good agreement, in general, with the worst discrepancy to be a factor of 3.6. We show that by including anharmonicities in the bound vibrational potentials to infinite order and calculating the energy levels by a uniform semiclassical prescription, the maximum error is reduced to 42%.

Authors:
 [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1492419
Report Number(s):
PNNL-SA-21771
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 98; Journal Issue: 9; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

McRae, Robin P., and Garrett, Bruce C. Anharmonic Corrections to Variational Transition State Theory Calculations of Rate Constants for a Model Activated Reaction in Solution. United States: N. p., 1993. Web. doi:10.1063/1.464760.
McRae, Robin P., & Garrett, Bruce C. Anharmonic Corrections to Variational Transition State Theory Calculations of Rate Constants for a Model Activated Reaction in Solution. United States. doi:10.1063/1.464760.
McRae, Robin P., and Garrett, Bruce C. Sat . "Anharmonic Corrections to Variational Transition State Theory Calculations of Rate Constants for a Model Activated Reaction in Solution". United States. doi:10.1063/1.464760. https://www.osti.gov/servlets/purl/1492419.
@article{osti_1492419,
title = {Anharmonic Corrections to Variational Transition State Theory Calculations of Rate Constants for a Model Activated Reaction in Solution},
author = {McRae, Robin P. and Garrett, Bruce C.},
abstractNote = {Previous errors in harmonic variational transition state theory calculations of rate constants for a model of an activated reaction in solution are corrected by including anharmonicities in the calculations of bound state energy levels. Harmonic variational transition state theory including multidimensional quantum mechanical corrections for reaction coordinate motion has previously been used to calculate the rate constant for a reaction model corresponding to a single solute coordinate coupled to a harmonic bath. Comparison of these rate constants with accurate quantum mechanical rate constants showed good agreement, in general, with the worst discrepancy to be a factor of 3.6. We show that by including anharmonicities in the bound vibrational potentials to infinite order and calculating the energy levels by a uniform semiclassical prescription, the maximum error is reduced to 42%.},
doi = {10.1063/1.464760},
journal = {Journal of Chemical Physics},
number = 9,
volume = 98,
place = {United States},
year = {1993},
month = {5}
}

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Cited by: 11 works
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