Photofragment angular momentum distributions from oriented and aligned polyatomic molecules: beyond the axial recoil limit

Abstract

A semi-classical theoretical treatment is presented for the description of photofragment polarization in the molecular frame, from the non-axial photodissociation of molecules which are oriented in the laboratory frame. Explicit expressions which quantify the experimental sensitivity to each of the polarization parameters, for prompt photodissociation, are given in terms of the non-axial-recoil deflection angles χ, α and ϕμd (which describe the orientation of the dipole and transition dipole moments about the recoil velocity), and the degree of the parent orientation and alignment. The application of this approach for the extraction of important dynamical information in the molecular frame is discussed, including cases where this information cannot be measured for isotropic samples of parent molecules.