Vibrational transition probabilities in photoelectron spectra

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Abstract
Variations in photoionization cross sections, or transition moments, over the vibrational envelope of photoelectron transitions are investigated. Differential photoionization cross sections within the orthogonalized plane‐wave approximation and Frank‐Condon factors using Morse oscillator vibrational wavefunctions are employed to calculate vibrational transition probabilities of photoelectron transitions. It is shown that cross sections for vibrational bands are a function of the kinetic energy of the ionized electrons and the average normal coordinates associated with specific vibrational‐photoelectron transitions. Calculated vibrational transition probabilities are compared to vibrational band intensities in the HeI(21.22 eV) and HeII(40.82 eV) photoelectron spectra of H2 and the HeI photoelectron spectrum of N2. The effect on the cross section of varying the kinetic energy of the photoelectron and the nuclear coordinates individually is investigated for H2, N2, and H2 O.

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