Optimal trajectory approach in the theory of photodissociation of thermally excited molecules

Abstract

The optimal trajectory (OT) approach is suggested to describe quantum effects in the direct photodissociation of thermally excited polyatomic molecules. OT represents a tunnel portion of a trajectory which minimizes the classical action (with eventual correction for the transition dipole moment) on the way from the well of the electronic ground state potential energy surface (PES) to the product PES. OT serves as a pilot steering the ground state density matrix to the “initial” density matrix on the excited PES which determines the product state distribution as a result of its evolution along the classical trajectory in the product channel.