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Proceedings Paper

Photoelectron spectroscopy with cm-1 resolution: VO+, benzyl+, toluene+
Author(s): James C. Weisshaar
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Paper Abstract

Detection of nominal `zero kinetic energy electrons' in resonant two-photon ionization with (omega) 1 fixed and (omega) 2 scanned permits photoelectron spectroscopy with 1 - 5 cm-1 resolution. We report vibrational bands from 0 - 650 cm-1 for benzyl+-h7, benzyl+-(alpha) d2, and benzyl+-d7. The exocyclic C-C bond of benzyl cation has substantial double bond character. Band assignments from ab initio frequencies illuminate the mechanism of vibronic coupling in the 12A2-22B2 system of neutral benzyl. In toluene+, we observe internal rotor frequencies that fix the V6 barrier height of the CH3 rotation at 20 +/- 5 cm-1, which is remarkably low. In VO yields VO+ + e-, we measure state-to-state relative photoionization cross sections from the intermediate spin-rotational state N' J' to different cation spin-rotation states N+J+. Remarkably strong lines corresponding to large changes in angular momentum ((Delta) N equals -6 to +7 and (Delta) J equals -6.5 to + 6.5) are observed. Accurate values of the adiabatic ionization potentials of each molecule are reported.

Paper Details

Date Published: 1 April 1992
PDF: 11 pages
Proc. SPIE 1638, Optical Methods for Time- and State-Resolved Chemistry, (1 April 1992); doi: 10.1117/12.58157
Show Author Affiliations
James C. Weisshaar, Univ. of Wisconsin/Madison (United States)


Published in SPIE Proceedings Vol. 1638:
Optical Methods for Time- and State-Resolved Chemistry
Cheuk-Yiu Ng, Editor(s)

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