ESR of $V(CO)_{n}$ (N=1 to 3)MOLECULES AT $4^{\circ} K$
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Date
1985
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Publisher
Ohio State University
Abstract
Vanadium carbonyls were produced by trapping vaporized vanadium metal in neon and argon matrices doped with small amounts of $^{12}CO$ and $^{13}CO$. Analyses of the X-band ESR spectra indicate that VCO has a $^{6}\Sigma$ ground state with a broad, relatively flat, potential. This is evidenced by two distinctly different sets of $^{51}V$ hyperfine splittings (hfs) and zero-field splittings $(|D|)$ in argon matrices. Only one of these molecules is trapped in neon. $^{13}C$ hfs is 6 G in both matrices. $V(CD)_{2}$ has a $^{4}\Sigma$ ground state with $|D| = 0.30 cm^{-1}$; the $^{13}C$ hfs is unresolved. A signal near $g = 2 \left(S = \frac{1}{2}\right)$ is assigned to $V(CD)_{3}$ with $D_{3h}$ or $C_{3v}$ symmetry. The trend among the three carbonyls is for $A_{iso}(51V),$ i.e., the unpaired s character, to decrease as n increases.
Description
Author Institution: Chemical Physics Center and Department of Chemistry, University of Florida; Chemical Physics Center and Department of Chemistry, University of Florida; Chemical Physics Center and Department of Chemistry, University of Florida