A direct approach to one photon interference contributions in the coherent control of photodissociation

Formally exact quantum mechanical expressions for cumulative transition matrix elements μjk(ξ,E)=∑n〈j|με|E,ξ,n−〉〈E,ξ,n−|με|k〉, central to one photon coherent control scenarios of photodissociation, are derived. The resultant approach bypasses the need for solving the complete state-to-state quantum mechanical reactive scattering problem to obtain control results. These exact expressions are implemented both quantum mechanically and via a semiclassical initial value representation method to investigate coherent control in the generic photodissociation of a triatomic into more than one product. The semiclassical approach is shown to provide an accurate description of bimolecular control in this system.