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EMISSION SPECTROSCOPY AND AB INITIO CALCULATIONS ON VCl AND VF

Author: Davis S. P.
Ram R. S.
Bernath P. F.
Lievin J.
Publication venue
Publication date: 01/01/2002
Field of study

Author Institution: Department of Chemistry, University of Arizona; Laboratoire de Chimie Physique Mol\'{e}culaire, Universit\'{e} Libre de Bruxelles; Department of Chemistry, University of Waterloo; Department of Physics, University of CaliforniaThe emission spectra of VCl and VF have been investigated in the

3400-17000 cm^{-1}

region using a Fourier transform spectrometer. The bands were excited in a high temperature carbon tube furnace from the reaction of vanadium metal vapors with

BCl_{3}

and

CF_{4}

, respectively. The VF bands were also observed in a microwave discharge through a flowing mixture of

VF_{4}

vapor and helium. The VCl bands with high wavenumber R heads near 6176.0, 6589.6, 7004.1, 7358.2 and

7710.0 cm^{-1}

have been assigned as the 0-2, 0-1, 0-0, 1-0 and 2-0 bands of the

[7.0]^{5}\Delta - X^{5}\Delta

electronic transition while the VF bands with R heads near 9156.8, 9816.4, 10481.4, 11035.8 and

11587.2 cm^{-1}

have been assigned as the 0-2, 0-1, 0-0, 1-0 and 2-0 bands, respectively, of the

[10.5]^{5}\Delta - X^{5}\Delta

transition. A rotational analysis of the

^{5}\Delta_{1} - ^{5}\Delta_{1}, ^{5}\Delta_{2} - ^{5}\Delta_{2}, ^{5}\Delta_{3} - ^{5}\Delta_{3}

and

^{5}\Delta_{4} - ^{5}\Delta_{4}

subbands of several bands of VCl and VF has been carried out and spectroscopic parameters have been obtained. Equilibrium constants of

\omega_{e}=417.37 cm^{-1}, \omega_{e}x_{e}=3.5 cm^{-1}, B_{e}=0.1658 cm^{-1}, \alpha_{e}=0.0006 cm^{-1}

and

r_{e}=2.2137

{\AA} have been obtained for the ground state of VCl, while equilibrium constants of

\Delta G(^{1}/_{2})=665.10 cm^{-1}, B_{e}=0.3863 cm^{-1}, \alpha_{e}=0.0028 cm^{-1}

and

r_{e}=1.7758

{\AA} have been determined for the ground state of VF. The spectroscopic properties of the low-lying electronic states of VCl have also been predicted by ab initio calculations. Our electronic assignments are supported by the results of our ab initio calculations