The classical Wigner method with an effective quantum force: application to the collinear H + H2 reaction

Huaqing Li; Jens Aage Poulsen; Gunnar Nyman

doi:10.1021/jp200886v

The classical Wigner method with an effective quantum force: application to the collinear H + H2 reaction

J Phys Chem A. 2011 Jun 30;115(25):7338-45. doi: 10.1021/jp200886v. Epub 2011 May 26.

Authors

Huaqing Li¹, Jens Aage Poulsen, Gunnar Nyman

Affiliation

¹ Department of Chemistry, University of Gothenburg, SE-412-96, Gothenburg, Sweden.

PMID: 21615109
DOI: 10.1021/jp200886v

Abstract

To improve the classical Wigner (CW) model, we recently proposed the classical Wigner model with an effective quantum force (CWEQF). The results of the CWEQF model are more accurate than those of the CW model. Still the simplicity of the CW model is retained. The quantum force was obtained by defining a characteristic distance η(0) between two Feynman paths that enter the expression for the flux-flux correlation function. η(0) was considered independent of the position along the reaction path. The CWEQF leads to a lowering of the effective potential barrier. Here we develop the method to use position dependent η(0) values. The method is also generalized to two dimensions. Applications are carried out on one-dimensional model problems and the two-dimensional H + H(2) collinear reaction.