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.