Rate constants from Monte Carlo quasi-classical trajectory calculations. A procedure for importance sampling

James Muckerman, M. B. Faist

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

The use of importance sampling as a variance reduction technique is applied to the direct Monte Carlo quasi-classical trajectory (MCQT) calculation of bimolecular gas phase rate constants. A general importance sampling function for the collision energy having a single (integer) parameter which characterizes the distribution of collision energies to be sampled is proposed and used in calculations of rate constants for three chemical reactions [F + H2, Cl + H2, and O(3P) + H2] at several temperatures. Results are compared with regard to accuracy and efficiency with rate constants obtained directly or indirectly using other MCQT approaches and the same potential energy surfaces. The importance sampling calculations are found to be more efficient over the entire range of reactivity studied, and provide statistically valid estimates of the errors in the computed rate constants.

Original languageEnglish
Pages (from-to)79-88
Number of pages10
JournalJournal of Physical Chemistry
Volume83
Issue number1
Publication statusPublished - 1979

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Importance sampling
Rate constants
sampling
Trajectories
trajectories
Potential energy surfaces
collisions
integers
Chemical reactions
chemical reactions
reactivity
Gases
potential energy
vapor phases
energy
estimates
Temperature
temperature

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Rate constants from Monte Carlo quasi-classical trajectory calculations. A procedure for importance sampling. / Muckerman, James; Faist, M. B.

In: Journal of Physical Chemistry, Vol. 83, No. 1, 1979, p. 79-88.

Research output: Contribution to journalArticle

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