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Updated: Jul 13, 2026

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
Published on: July 27, 2018
Quasibound continuum states in SiF4 (D2A1) photoionization: photoelectron-vibrational coupling
Raffaele Montuoro1, Robert R Lucchese, John D Bozek
1Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, USA.
Abstract:
The authors report a fully vibrationally resolved photoelectron spectroscopy investigation of a nonplanar molecule studied over a range of excitation energies. Experimental results for all four fundamental vibrational modes are presented. In each case significant non-Franck-Condon effects are seen. The vibrational branching ratio for the totally symmetric mode nu1+ is found to be strongly affected by resonant excitation in the SiF4+ (D2A1) photoionization channel. This is shown to be the result of two distinct shape resonances, which for the first time have been both confirmed by theoretical calculations. Vibrationally resolved Schwinger photoionization calculations are used to understand the vibronic coupling for the photoelectrons, both using ab initio and harmonic vibrational wave functions.
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Stretching vibrations are vibrational motions that occur along the bond line, changing the bond length or distance between two bonded atoms. They are further distinguished as symmetric or asymmetric. In symmetric stretching, the...

