A full-dimensional analytical potential energy surface for the F+CH4→HF+CH3 reaction

doi:10.1088/1674-1056/22/6/063102

Abstract A full-dimensional analytical potential energy surface (APES) for the F+CH₄→HF +CH₃ reaction is developed based on 7127 ab initio energy points at the unrestricted coupled-cluster with single, double, and perturbative triple excitations. The correlation-consistent polarized triple-split valence basis set is used. The APES is represented with a many-body expansion containing 239 parameters determined by the least square fitting method. The two-body terms of the APES are fitted by potential energy curves with multi-reference configuration interaction, which can describe the diatomic molecules (CH, H₂, HF, and CF) accurately. It is found that the APES can reproduce the geometry and vibrational frequencies of the saddle point better than those available in the literature. The rate constants based on the present APES support the experimental results of Moore et al. [Int. J. Chem. Kin. 26, 813 (1994)]. The analytical first-order derivation of energy is also provided, making the present APES convenient and efficient for investigating the title reaction with quasiclassical trajectory calculations.

Keywords: analytical potential energy surface least square fitting method UCCSD(T) F+CH₄→HF+CH₃ reaction

Received: 17 October 2012
Revised: 28 November 2012
Accepted manuscript online:

PACS:	31.50.-x	(Potential energy surfaces)
	31.50.Bc	(Potential energy surfaces for ground electronic states)
	82.20.Kh	(Potential energy surfaces for chemical reactions)

Fund: Project supported by the National Natural Science Foundation of China (Grant Nos. 11174117 and 10974078).

Corresponding Authors: Yang Chuan-Lu
E-mail: scuycl@gmail.com

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Yang Chuan-Lu (杨传路), Wang Mei-Shan (王美山), Liu Wen-Wang (刘文旺), Zhang Zhi-Hong (张志红), Ma Xiao-Guang (马晓光) A full-dimensional analytical potential energy surface for the F+CH₄→HF+CH₃ reaction 2013 Chin. Phys. B 22 063102

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A full-dimensional analytical potential energy surface for the F+CH4→HF+CH3 reaction

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A full-dimensional analytical potential energy surface for the F+CH₄→HF+CH₃ reaction