Thermal flux based analysis of state-to-state reaction probabilities

Abstract

Flux correlation functions facilitate rigorous quantum mechanical calculations of reaction rates and initial state-selected reaction probabilities. Combined with an efficient multi-dimensional wave packet propagation employing the multi-configurational time-dependent Hartree scheme, polyatomic reactions can be accurately studied. Very recently, the approach has been generalized to the treatment of fully resolved state-to-state reaction probabilities. The generalized flux correlation function employed utilizes two flux operators corresponding to a dividing surface located in the transition state region and two additional dividing surfaces located in the reactant and product asymptotic areas. The present work provides further analysis of this generalized flux correlation function. It studies state-to-state reaction probabilities of the D + H2(ν, j) → HD(ν′, j′) + H reaction for J = 0 and investigates the contributions of the different thermal flux eigenstate pairs, which correspond to vibrational states of the activated complex.