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Updated: Apr 7, 2026

Angle-resolved Photoemission Spectroscopy At Ultra-low Temperatures
Published on: October 9, 2012
High-Resolution Photoelectron Spectroscopy of Cryogenically Cooled VO3H2
Korina Vlahos1, Martin DeWitt1, Daniel M Neumark1
1Department of Chemistry, University of California, Berkeley, California 94720, United States.
Abstract:
High-resolution photoelectron spectra of cryogenically cooled VO3H2- anions obtained with slow electron velocity-map imaging (cryo-SEVI) are reported. Comparison with DFT calculations shows that the spectra are from the cis-VO(OH)2- dissociative adduct. The same complex is formed through either the VO2- + H2O or VO3- + H2 pathways, with the latter yielding significantly more ions. The experiment yields an electron affinity of 1.857(1) eV and several vibrational frequencies for the neutral species. Comparisons to Franck-Condon (FC) simulations show good agreement with the experimental features, but there are several transitions that do not appear in the simulations. These features are assigned to FC-forbidden transitions involving nontotally symmetric vibrational modes and are attributed to Herzberg-Teller (HT) coupling with the excited C̃1B2 anion state. The results are compared to the previous (cryo-SEVI) study of the titania water-split adduct, TiO3H2- to explore the role of the additional vanadium valence electron in the spectroscopy and chemistry of these adducts.
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