Fine- and hyperfine-structure effects in molecular photoionization. I. General theory and direct photoionization
- Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel (Switzerland)
We develop a model for predicting fine- and hyperfine intensities in the direct photoionization of molecules based on the separability of electron and nuclear spin states from vibrational-electronic states. Using spherical tensor algebra, we derive highly symmetrized forms of the squared photoionization dipole matrix elements from which we derive the salient selection and propensity rules for fine- and hyperfine resolved photoionizing transitions. Our theoretical results are validated by the analysis of the fine-structure resolved photoelectron spectrum of O{sub 2} reported by Palm and Merkt [Phys. Rev. Lett. 81, 1385 (1998)] and are used for predicting hyperfine populations of molecular ions produced by photoionization.
- OSTI ID:
- 22679056
- Journal Information:
- Journal of Chemical Physics, Vol. 145, Issue 4; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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