Bond length and electronic structure of V/sub 2/

Journal Article · Sun Jan 15 00:00:00 EST 1984 · J. Chem. Phys.; (United States)

OSTI ID:5462478

Langridge-Smith, P R.R.; Morse, M D; Hansen, G P; Smalley, R E; Merer, A J

We report of the first gas-phase electronic spectrum of V/sub 2/. 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 A was observed. Rotationally resolved spectra of this band system conclusively demonstrate that the transition is of the type /sup 3/Pi/sub u/(a)reverse arrow/sup 3/..sigma../sup -//sub g/(a), and we assign the /sup 3/..sigma../sup -//sub g/ state as the ground electronic state of V/sub 2/. The short ground state bond length r/sub e//sup double-prime/ = 1.77 A and high vibrational frequency ..omega../sub e//sup double-prime/ = 535 cm/sup -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 /sup 3/..sigma../sup -//sub g/ state implies that the ground state electronic configuration contains a half-filled ..pi..(3d) or delta (3d) orbital. The most plausible valence configuration consistent with the data is sigma/sub g/(3d)/sup 2/..pi../sub u/(3d)/sup +/sigma/sub g/(4s)/sup 2/delta/sub g/(3d)/sup 2/. In the excited state there is strong evidence of predissociation occuring for levels higher than 14 872 cm/sup -1/ above the ground state, thus providing an upper bound of 1.85 eV for the dissociation energy of V/sub 2/.

• Research Organization: Rice Quantum Institute and Department of Chemistry, Rice University, Houston, Texas 77251
• OSTI ID: 5462478
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 80:2; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
BOND LENGTHS
DIMENSIONS
DIMERS
DISSOCIATION ENERGY
ELECTROMAGNETIC RADIATION
ELECTRONIC STRUCTURE
ELEMENTS
ENERGY
EVAPORATION
LASER RADIATION
LENGTH
METALS
PHASE TRANSFORMATIONS
RADIATIONS
SPECTRA
TRANSITION ELEMENTS
VANADIUM
VISIBLE SPECTRA