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 language | English |
|---|---|
| Pages (from-to) | 79-88 |
| Number of pages | 10 |
| Journal | Journal of Physical Chemistry |
| Volume | 83 |
| Issue number | 1 |
| Publication status | Published - 1979 |
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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 journal › Article
}
TY - JOUR
T1 - Rate constants from Monte Carlo quasi-classical trajectory calculations. A procedure for importance sampling
AU - Muckerman, James
AU - Faist, M. B.
PY - 1979
Y1 - 1979
N2 - 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.
AB - 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.
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M3 - Article
VL - 83
SP - 79
EP - 88
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 1
ER -