Semiclassical molecular dynamics simulations of ultrafast photodissociation dynamics associated with the Chappuis band of ozone

In this paper we investigate the nonadiabatic ultrafast dynamics of interconversion between the two lower lying excited states of ${}^1{A}^{″}$ symmetry (1 ${}^1{A}^{″}$ and 2 ${}^1{A}^{″})$ of ozone following photoexcitation of the molecule in the gas phase with visible light. Our algorithm involves a semiclassical initial value representation method which is able to describe electronically nonadiabatic processes within the time dependent picture through the quantization of the classical electron–nuclear model Hamiltonian of Meyer and Miller [J. Chem. Phys. 70, 7 (1979)]. We explore the capabilities of these techniques as applied to studying the dynamics of a realistic reaction of photodissociation on full ab initio electronic potential energy surfaces. Our semiclassical results provide an intuitive understanding of the most fundamental dynamical features involved in the process of predissociation, such as decay and recurrence events, as well as an interpretation of experimental studies of the Chappuis band of ozone in the frequency domain.