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

Abstract

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 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${}_2$ (reported by H. Palm and F. Merkt, Phys. Rev. Lett. 81, 1385 (1998)) and are used for predicting hyperfine populations of molecular ions produced by photoionization.

References in corpus (1)

• Fine- and hyperfine-structure effects in molecular photoionization: II. Resonance-enhanced multiphoton ionization and hyperfine-selective generation of molecular cations

Cited by in corpus (7)

• Two-photon vibrational transitions in ${\mathrm{O}}_2^{+}$ as probes of variation of the proton-to-electron mass ratio
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• State-selective coherent motional excitation as a new approach for the manipulation, spectroscopy and state-to-state chemistry of single molecular ions
• Fine- and hyperfine-structure effects in molecular photoionization: II. Resonance-enhanced multiphoton ionization and hyperfine-selective generation of molecular cations
• Cold CH radicals for laser cooling and trapping
• State Selective Preparation and Nondestructive Detection of Trapped ${\mathrm{O}}_2^{+}$
• Rotational excitation in sympathetic cooling of diatomic molecular ions by laser-cooled atomic ions