The bond length and electronic structure of V2
10.1063/1.446769
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

We report of the first gas-phase electronic spectrum of V2. The dimer was generated in an expansion cooled molecular beam by laser vaporization of vanadium metal. Using the technique of resonant two photon ionization spectroscopy a strong band system with origin near 7000 Å was observed. Rotationally resolved spectra of this band system conclusively demonstrate that the transition is of the type 3Πu(a)←3Σ−g(a), and we assign the 3Σ−g state as the ground electronic state of V2. The short ground state bond length re″=1.77 Å and high vibrational frequency ωe″=535 cm−1 are indicative of extensive 3d-orbital participation in the bonding of this molecule. The unusual case (a) coupling and large second-order spin-orbit splitting observed in the 3Σ−g state implies that the ground state electronic configuration contains a half-filled π(3d) or δ (3d) orbital. The most plausible valence configuration consistent with the data is σg(3d)2πu(3d)+σg(4s)2δg(3d)2. In the excited state there is strong evidence of predissociation occuring for levels higher than 14 872 cm−1 above the ground state, thus providing an upper bound of 1.85 eV for the dissociation energy of V2.

Bibliography

Langridge-Smith, P. R. R., Morse, M. D., Hansen, G. P., Smalley, R. E., & Merer, A. J. (1984). The bond length and electronic structure of V2. The Journal of Chemical Physics, 80(2), 593–600.

Authors 5
  1. P. R. R. Langridge-Smith (first)
  2. M. D. Morse (additional)
  3. G. P. Hansen (additional)
  4. R. E. Smalley (additional)
  5. A. J. Merer (additional)
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Dates
Type When
Created 22 years, 6 months ago (Feb. 28, 2003, 12:18 p.m.)
Deposited 1 year, 6 months ago (Feb. 9, 2024, 8:47 p.m.)
Indexed 1 week, 2 days ago (Aug. 26, 2025, 2:46 a.m.)
Issued 41 years, 7 months ago (Jan. 15, 1984)
Published 41 years, 7 months ago (Jan. 15, 1984)
Published Print 41 years, 7 months ago (Jan. 15, 1984)
Funders 0

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@article{Langridge_Smith_1984, title={The bond length and electronic structure of V2}, volume={80}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.446769}, DOI={10.1063/1.446769}, number={2}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Langridge-Smith, P. R. R. and Morse, M. D. and Hansen, G. P. and Smalley, R. E. and Merer, A. J.}, year={1984}, month=jan, pages={593–600} }