Helicity decoupled quantum dynamics and capture model cross sections and rate constants for O(1D) + H2 → OH + H

Stephen K. Gray, Evelyn M. Goldfield, George C Schatz, Gabriel G. Balint-Kurti

Research output: Contribution to journalArticle

108 Citations (Scopus)

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 languageEnglish
Pages (from-to)1141-1148
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume1
Issue number6
DOIs
Publication statusPublished - Mar 15 1999

Fingerprint

Rate constants
Angular momentum
cross sections
angular momentum
Trajectories
trajectories
Wave packets
Potential energy surfaces
approximation
wave packets
potential energy
orbitals
Temperature
room temperature
electronics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

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 journalArticle

Gray, Stephen K. ; Goldfield, Evelyn M. ; Schatz, George C ; Balint-Kurti, Gabriel G. / Helicity decoupled quantum dynamics and capture model cross sections and rate constants for O(1D) + H2 → OH + H. In: Physical Chemistry Chemical Physics. 1999 ; Vol. 1, No. 6. pp. 1141-1148.
@article{f07a7fcfad80488c862403fa9fbdd483,
title = "Helicity decoupled quantum dynamics and capture model cross sections and rate constants for O(1D) + H2 → OH + H",
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.",
author = "Gray, {Stephen K.} and Goldfield, {Evelyn M.} and Schatz, {George C} and Balint-Kurti, {Gabriel G.}",
year = "1999",
month = "3",
day = "15",
doi = "10.1039/a809325c",
language = "English",
volume = "1",
pages = "1141--1148",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "6",

}

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.

UR - http://www.scopus.com/inward/record.url?scp=0033559699&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0033559699&partnerID=8YFLogxK

U2 - 10.1039/a809325c

DO - 10.1039/a809325c

M3 - Article

AN - SCOPUS:0033559699

VL - 1

SP - 1141

EP - 1148

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 6

ER -