Determination of all scattering phases and amplitudes in the photodissociation of a diatomic molecule

Abstract

Analysis of the rank K=0-3 anisotropy (orientation and alignment) parameters describing the angular momentum polarization of the Cl atoms formed from the 467 nm photodissociation of BrCl enables the relative phases and the amplitudes of the nuclear wavefunctions to be obtained for all of the five adiabatic potential energy curves with Ω =0+ and 1 correlating to the lowest dissociation limit. A so-called ‘complete’ experiment is thus demonstrated for photodissociation of this diatomic molecule in which all the components of the photofragmentation T-matrix are derived. Quantification of the amplitudes of dissociative flux on the , A3Π1, B3Π0+, C1Π1 and D(1) states demonstrates the importance of non-adiabaticity in the dissociation dynamics. The relative phases contain contributions arising from nuclear motion on potential energy curves of different shapes in the short-range region, and from dynamical phase shifts associated with non-adiabatic transitions.