THEORY OF THE ANGULAR DISTRIBUTION PROBLEM IN MOLECULAR PHOTOELECTRON SPECTROSCOPY.
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Date
1969
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Publisher
Ohio State University
Abstract
A theory of the angular distribution of photoelectrons ejected from diatomic molecules in a photoelectron spectroscopy experiment has been formulated. For electric-diple transitions the differential cross-section $\sigma_{\Omega}$ is of the form $ \sigma_{\Omega} = (\sigma_{total}/4\pi)[1 + \beta P_{2}(\cos \theta)]$ Where $\sigma_{total}$ is the total cross-section, $\beta$ an anisotropy parameter, and $\theta$ the angle between the polarization vector of the incident light and the direction of the photoelectron. Expressions for $\sigma_{total}$ and $\beta$ in terms of internal transition dipoles have been obtained for transitions between individual rotational states of the molecule and ion, for either of Hund's cases (a) or (b). When rotational structure in the photoelectron spectrum is unresolved the angular distribution is independent of the choice of Hund's case. The theory suggests how, in favourable cases, measurements of angular distributions might yield information regarding (1) the molecular orbital from which the photoelectron is ejected and (2) the radial part of the photoelectron eigenfunction.
Description
Present address of B.J. Orr: Division of Pure Physics, National Research Council of Canada, Ottawa, Ontario.
Author Institution: Department of Theorectical Chemistry, University of Bristol
Author Institution: Department of Theorectical Chemistry, University of Bristol