Abstract
We study, within a helicity decoupled quantum approximation, the total angular momentum J dependence of reaction probabilities for the reaction O(1D) + H2 → OH + H. A recently developed real wave packet approach is employed for the quantum calculations. The ab initio based, ground electronic (X̄ 1A') potential energy surface of Ho et al. (T-S. Ho, T. Hollebeeck, H. Rabitz, L. B. Harding and G. C. Schatz, J. Chem. Phys., 1996, 105, 10472) is assumed for most of our calculations, although some calculations are also performed with a recent surface due to Dobbyn and Knowles. We find that the low J reaction probabilities tend to be, on average, slightly lower than the high J probabilities. This effect is also found to be reproduced in classical trajectory calculations. A new capture model is proposed that incorporates the available quantum data within an orbital angular momentum or l-shifting approximation to predict total cross sections and rate constants. The results agree well with classical trajectory results and the experimental rate constant at room temperature. However, electronically non-adiabatic effects may become important at higher temperature.
| Original language | English |
|---|---|
| Pages (from-to) | 1141-1148 |
| Number of pages | 8 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 1 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - Mar 15 1999 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Atomic and Molecular Physics, and Optics
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Helicity decoupled quantum dynamics and capture model cross sections and rate constants for O(1D) + H2 → OH + H. / Gray, Stephen K.; Goldfield, Evelyn M.; Schatz, George C; Balint-Kurti, Gabriel G.
In: Physical Chemistry Chemical Physics, Vol. 1, No. 6, 15.03.1999, p. 1141-1148.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Helicity decoupled quantum dynamics and capture model cross sections and rate constants for O(1D) + H2 → OH + H
AU - Gray, Stephen K.
AU - Goldfield, Evelyn M.
AU - Schatz, George C
AU - Balint-Kurti, Gabriel G.
PY - 1999/3/15
Y1 - 1999/3/15
N2 - We study, within a helicity decoupled quantum approximation, the total angular momentum J dependence of reaction probabilities for the reaction O(1D) + H2 → OH + H. A recently developed real wave packet approach is employed for the quantum calculations. The ab initio based, ground electronic (X̄ 1A') potential energy surface of Ho et al. (T-S. Ho, T. Hollebeeck, H. Rabitz, L. B. Harding and G. C. Schatz, J. Chem. Phys., 1996, 105, 10472) is assumed for most of our calculations, although some calculations are also performed with a recent surface due to Dobbyn and Knowles. We find that the low J reaction probabilities tend to be, on average, slightly lower than the high J probabilities. This effect is also found to be reproduced in classical trajectory calculations. A new capture model is proposed that incorporates the available quantum data within an orbital angular momentum or l-shifting approximation to predict total cross sections and rate constants. The results agree well with classical trajectory results and the experimental rate constant at room temperature. However, electronically non-adiabatic effects may become important at higher temperature.
AB - We study, within a helicity decoupled quantum approximation, the total angular momentum J dependence of reaction probabilities for the reaction O(1D) + H2 → OH + H. A recently developed real wave packet approach is employed for the quantum calculations. The ab initio based, ground electronic (X̄ 1A') potential energy surface of Ho et al. (T-S. Ho, T. Hollebeeck, H. Rabitz, L. B. Harding and G. C. Schatz, J. Chem. Phys., 1996, 105, 10472) is assumed for most of our calculations, although some calculations are also performed with a recent surface due to Dobbyn and Knowles. We find that the low J reaction probabilities tend to be, on average, slightly lower than the high J probabilities. This effect is also found to be reproduced in classical trajectory calculations. A new capture model is proposed that incorporates the available quantum data within an orbital angular momentum or l-shifting approximation to predict total cross sections and rate constants. The results agree well with classical trajectory results and the experimental rate constant at room temperature. However, electronically non-adiabatic effects may become important at higher temperature.
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U2 - 10.1039/a809325c
DO - 10.1039/a809325c
M3 - Article
VL - 1
SP - 1141
EP - 1148
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 6
ER -