TY - JOUR
T1 - Pulsed field ionization zero kinetic energy photoelectron spectroscopy of the vanadium dimer molecule
AU - Yang, Dong Sheng
AU - James, Andrew M.
AU - Rayner, David M.
AU - Hackett, Peter A.
PY - 1995
Y1 - 1995
N2 - 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).
AB - 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).
UR - http://www.scopus.com/inward/record.url?scp=36449002677&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=36449002677&partnerID=8YFLogxK
U2 - 10.1063/1.468623
DO - 10.1063/1.468623
M3 - Article
AN - SCOPUS:36449002677
SN - 0021-9606
VL - 102
SP - 3129
EP - 3134
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 8
ER -