Non-adiabatic reactive routes and the applicability of multiconfiguration time-dependent self-consistent field approximations

Abstract

A time-dependent non-adiabatic formulation is considered for chemical reactions. Basic algorithms are presented for the photodissociation of CH₃I under the influence of strong short laser pulses. Detailed insight into the dynamics of this process is demonstrated. A time-dependent self-consistent field approach is suggested when many degrees of freedom have to be considered simultaneously. The derivation is based on a Liouville space description for which quantum and classical mechanics are treated on equal grounds. A multiconfiguration approach is formulated for explicitly including correlation due to splitting of the probability density and for non-adiabatic motion.