An atomic diffraction theory of molecular photoionization cross sections

Abstract A theory of molecular photoionization cross sections is developed on the basis of locally atomic character of the one-electron final state in the Golden Rule expression for the molecular orbital cross section. Ionization amplitudes from several atomic centres are added and rotationally averaged to produce molecular orbital cross sections displaying a sum of pseudo-atomic cross sections weighted according to the LCAO composition of the orbital and also two-centre products reflecting interference effects. The atomic ionization amplitudes are obtained by use of an atomic central potential constructed by an inversion procedure from the form of the ground state orbital. The theory is of a simple chemical nature but usually of at least semi-quantitative accuracy. In this work we illustrate the nature of the two-centre interference effects in small diatomic molecules (H 2 , HF, N 2 ).