Pulsed field ionization zero kinetic energy photoelectron spectroscopy of the vanadium dimer molecule

Dong Sheng Yang, Andrew M. James, David M. Rayner, Peter A. Hackett

Research output: Contribution to journalArticlepeer-review

51 Scopus citations

Abstract

The technique of pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE), photoelectron spectroscopy was employed to probe the electronic structure of the V2+ cation. Rotationally resolved PFI-ZEKE spectra of the V2+ ground state were obtained by two color excitation via the 700 nm A 3Πu←X 3Σ g- system. The observation of transitions from the A 3Π2u state to two spin-orbit components with Ω=1/2 and Ω=3/2, confirms that the cation ground state has 4Σg- symmetry, in accordance with previous experimental and theoretical work. Striking differences were observed in the rotational selection rules for the 4Σg -←A 3Π1u and the 4Σ g1←A 3Π2u transitions. The adiabatic ionization potential of V2 was determined to be 51 271.14(50) cm-1. From an analysis of the rotational structure of the PFI-ZEKE spectra, the following molecular constants were determined for the 4Σg1 state: r0=1.7347(24) Å, second order spin-orbit splitting, λ=5.248(17) cm-1, spin-rotation constant, γ=0.0097(87) cm-1, T0=51 282.20(50) cm-1 (1σ error bounds).

Original languageEnglish
Pages (from-to)3129-3134
Number of pages6
JournalJournal of Chemical Physics
Volume102
Issue number8
DOIs
StatePublished - 1995

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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