MRCI calculations of the lowest potential energy surface for CH 3OH and direct ab initio dynamics simulations of the O( 1D) + CH 4 reaction

Hua Gen Yu, James Muckerman

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50 Citations (Scopus)

Abstract

The stationary point geometries and frequencies on the lowest singlet potential energy surface for the CH 3OH system are calculated using the complete-active-space self-consistent-field method. The energetics are refined using a restricted internally contracted multireference configuration interaction (MRCI) method at the complete basis set (CBS) limit. The CBS energy is extrapolated using the scheme of Halkier et al. with two large basis sets: aug-cc-pVDZ and aug-cc-pVTZ. The implications of our calculated results concerning the O( 1D) + CH 4 and OH + CH 3 reactions are discussed. In addition, the O( 1D) + CH 4 reaction at a collision energy of 6.8 kcal/mol is investigated using a variant of the "scaling all correlation" (SAC) method of Truhlar et al. and the coupled-cluster double-excitation (CCD) method in a direct dynamics study with a D95(d,p) basis set. The results show that the O( 1D) + CH 4 → OH + CH 3 reaction occurs both via direct and long-lived intermediate pathways. The differential cross section for the direct reaction to form OH is forward peaked with a nearly Isotropic background. Finally, the branching fractions for OH, H, H 2, and H 2O are predicted to be 0.725:0.186:0.025:0.064.

Original languageEnglish
Pages (from-to)8615-8623
Number of pages9
JournalJournal of Physical Chemistry A
Volume108
Issue number41
DOIs
Publication statusPublished - Oct 14 2004

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Potential energy surfaces
Correlation methods
configuration interaction
potential energy
methylidyne
Geometry
Computer simulation
simulation
self consistent fields
scaling
collisions
energy
cross sections
geometry
excitation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "MRCI calculations of the lowest potential energy surface for CH 3OH and direct ab initio dynamics simulations of the O( 1D) + CH 4 reaction",
abstract = "The stationary point geometries and frequencies on the lowest singlet potential energy surface for the CH 3OH system are calculated using the complete-active-space self-consistent-field method. The energetics are refined using a restricted internally contracted multireference configuration interaction (MRCI) method at the complete basis set (CBS) limit. The CBS energy is extrapolated using the scheme of Halkier et al. with two large basis sets: aug-cc-pVDZ and aug-cc-pVTZ. The implications of our calculated results concerning the O( 1D) + CH 4 and OH + CH 3 reactions are discussed. In addition, the O( 1D) + CH 4 reaction at a collision energy of 6.8 kcal/mol is investigated using a variant of the {"}scaling all correlation{"} (SAC) method of Truhlar et al. and the coupled-cluster double-excitation (CCD) method in a direct dynamics study with a D95(d,p) basis set. The results show that the O( 1D) + CH 4 → OH + CH 3 reaction occurs both via direct and long-lived intermediate pathways. The differential cross section for the direct reaction to form OH is forward peaked with a nearly Isotropic background. Finally, the branching fractions for OH, H, H 2, and H 2O are predicted to be 0.725:0.186:0.025:0.064.",
author = "Yu, {Hua Gen} and James Muckerman",
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N2 - The stationary point geometries and frequencies on the lowest singlet potential energy surface for the CH 3OH system are calculated using the complete-active-space self-consistent-field method. The energetics are refined using a restricted internally contracted multireference configuration interaction (MRCI) method at the complete basis set (CBS) limit. The CBS energy is extrapolated using the scheme of Halkier et al. with two large basis sets: aug-cc-pVDZ and aug-cc-pVTZ. The implications of our calculated results concerning the O( 1D) + CH 4 and OH + CH 3 reactions are discussed. In addition, the O( 1D) + CH 4 reaction at a collision energy of 6.8 kcal/mol is investigated using a variant of the "scaling all correlation" (SAC) method of Truhlar et al. and the coupled-cluster double-excitation (CCD) method in a direct dynamics study with a D95(d,p) basis set. The results show that the O( 1D) + CH 4 → OH + CH 3 reaction occurs both via direct and long-lived intermediate pathways. The differential cross section for the direct reaction to form OH is forward peaked with a nearly Isotropic background. Finally, the branching fractions for OH, H, H 2, and H 2O are predicted to be 0.725:0.186:0.025:0.064.

AB - The stationary point geometries and frequencies on the lowest singlet potential energy surface for the CH 3OH system are calculated using the complete-active-space self-consistent-field method. The energetics are refined using a restricted internally contracted multireference configuration interaction (MRCI) method at the complete basis set (CBS) limit. The CBS energy is extrapolated using the scheme of Halkier et al. with two large basis sets: aug-cc-pVDZ and aug-cc-pVTZ. The implications of our calculated results concerning the O( 1D) + CH 4 and OH + CH 3 reactions are discussed. In addition, the O( 1D) + CH 4 reaction at a collision energy of 6.8 kcal/mol is investigated using a variant of the "scaling all correlation" (SAC) method of Truhlar et al. and the coupled-cluster double-excitation (CCD) method in a direct dynamics study with a D95(d,p) basis set. The results show that the O( 1D) + CH 4 → OH + CH 3 reaction occurs both via direct and long-lived intermediate pathways. The differential cross section for the direct reaction to form OH is forward peaked with a nearly Isotropic background. Finally, the branching fractions for OH, H, H 2, and H 2O are predicted to be 0.725:0.186:0.025:0.064.

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