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J Chem Phys. 2016 Jul 28;145(4):044314. doi: 10.1063/1.4955301.

Fine- and hyperfine-structure effects in molecular photoionization. I. General theory and direct photoionization.

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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 O2 reported by Palm and Merkt [Phys. Rev. Lett. 81, 1385 (1998)] and are used for predicting hyperfine populations of molecular ions produced by photoionization.


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