Photoelectron spectroscopy with cm-1 resolution: VO+, benzyl+, toluene+

James C. Weisshaar

doi:10.1117/12.58157

1 April 1992 Photoelectron spectroscopy with cm^-1 resolution: VO⁺, benzyl⁺, toluene⁺

James C. Weisshaar

Proceedings Volume 1638, Optical Methods for Time- and State-Resolved Chemistry; (1992) https://doi.org/10.1117/12.58157
Event: OE/LASE '92, 1992, Los Angeles, CA, United States

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.

Citation Download Citation

James C. Weisshaar "Photoelectron spectroscopy with cm^-1 resolution: VO⁺, benzyl⁺, toluene⁺", Proc. SPIE 1638, Optical Methods for Time- and State-Resolved Chemistry, (1 April 1992); https://doi.org/10.1117/12.58157

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