A Discussion on photoelectron spectroscopy - Angular distributions and intensity in molecular photoelectron spectroscopy I. General theory for diatomic molecules

Abstract A theory of the angular distribution of photoelectrons ejected with a given energy from diatomic molecules is presented. The differential cross-section OO is of the form a = ^ [l+ /JP ,(co»® )] where O Total is the total cross-section, B an anisotropy parameter and O the angle between the polarization vector of the incident light and the direction of the photoelectron. Expressions for O total and B in terms of internal transition dipole moments are obtained for transitions between individual rotational states of the molecule and ion, for either of Hund’s cases (a) or (b) . The formulae have been developed for central-field bases for the eigenstates of the electron before and after ionization. When rotational structure in the photoelectron spectrum is unresolved the angular distribution is independent of the choice of Hund’s case