Quantum mechanical wave packet and quasiclassical trajectory calculations for the Li + H2(+) reaction

N Bulut; J F Castillo; L Bañares; F J Aoiz

doi:10.1021/jp904429e

Quantum mechanical wave packet and quasiclassical trajectory calculations for the Li + H2(+) reaction

J Phys Chem A. 2009 Dec 31;113(52):14657-63. doi: 10.1021/jp904429e.

Authors

N Bulut¹, J F Castillo, L Bañares, F J Aoiz

Affiliation

¹ Departamento de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain.

PMID: 19621933
DOI: 10.1021/jp904429e

Abstract

The dynamics and kinetics of the Li + H2(+) reaction have been studied by means of quantum mechanical (QM) real wave packet, wave packet with flux operator, and quasiclassical trajectory (QCT) calculations on the ab initio potential energy surface of Martinazzo et al. [J. Chem. Phys., 2003, 119, 21]. Total initial state-selected reaction probabilities for the title reaction have been calculated for total angular momentum J = 0 at collision energies from threshold up to 1 eV. Wave packet reaction probabilities at selected values of the total angular momentum up to J = 60 are obtained using the centrifugal sudden approximation (CSA). Integral cross sections and rate constants have been calculated from the wave packet reactions probabilities by means of a refined J-shifting method and the separable rotation approximation in combination with the CSA for J > 0. The calculated rate constants as function of temperature show an Arrhenius type behavior. The QM results are found to be in overall good agreement with the corresponding QCT data.