Photodissociation and continuum resonance Raman cross sections and general Franck–Condon intensities from S-matrix Kohn scattering calculations with application to the photoelectron spectrum of H2F−+hν→H2+F, HF+H + e−

Abstract

It is shown how the S-matrix version of the Kohn variational method for quantum scattering can be readily adapted to compute matrix elements involving the scattering wave function and also matrix elements of the scattering Green’s function. The former of these quantities is what is involved in computing photodissociation cross sections, photodetachment intensities from a bound negative ion to a neutral scattering state, or the intensity of any Franck–Condon transition from a bound state to a scattering state. The latter quantity (i.e., a matrix element of the scattering Green’s function between two bound states) gives the resonance Raman cross section for the case that the intermediate state in the Raman process is a scattering state. Once the basic S-matrix Kohn scattering calculation has been performed, it is shown that little additional effort is required to determine these quantities. Application of this methodology is made to determine the electron energy distribution for photodetachment of H2F− to F+H2, HF+H. Resonance structure in the J=0 reaction probabilities is seen to appear in the electron energy distribution.