OPTICAL STARK AND PUMP/PROBE MICROWAVE OPTICAL DOUBLE RESONANCE SPECTROSCOPY OF GAS-PHASE CHROMIUM MONONITRIDE AND VANADIUM MONONITRIDE

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1998

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Ohio State University

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High resolution optical spectroscopic studies of gas-phase chromium mononitride, CrN, and vanadium mononitride, VN, using molecular beam techniques have been performed. The $R_{ee}(0.5)$ branch feature of the $(0,0)A^{4}\Pi_{3/2}-A^{4}\Sigma^{-}_{1/2}$ band system for $^{52}CrN$ was recorded as a function of the static electric field in the range $1.2 - 2.0$ kV/cm. The resultant Stark shifts were analyzed to produce permanent electric dipole moments of 2.31(4)D and 5.41(2)D for the ground $X^4\Sigma^{-}_{1/2}$ and excited $A^{4}II_{3/2}$ states, respectively. The $P_{e}, F^{\prime \prime} = 2.5$ feature of the $(0,0) D^{3}\Pi_{0}- X^{3} \Delta_{1}$ band system for $^{51}V^{14}N (I=3.5)$ was also recorded as a function of static electric field in the range .4 - 1.2 kV/cm. The permanent electric dipole moments derived from a least squares analysis of the Stark shifts were 3.07(1)D for the ground $X^{3}\Delta_{1}$ state and 6.15(3)D for the excited $D^{3}\Pi_{0}$ state. The $^{52}Cr^{14}N (I=1)$ hyperfine structure was determined from the analysis of 12 components of the lowest pure rotational levels using the pump/probe microwave-optical double resonance technique. The resulting parameters are (in $cm^{-1}) B^{\prime \prime}=.62387360(74), B^{\prime}= .6060(1), \gamma^{\prime \prime}=.0070050(13), \lambda^{\prime \prime}= 2.611151(16), eqQ_{0}(^{14}N)=-.000025(10),b_{F}(^{14}N)= .0000062(34)$ and $c(^{14}N)=-.000151(92)$. Comparisons to other experimental work and theoretical bonding models are $given^{a}$. Observed trends amongst the early transition metals will be discussed.

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$^{a}$ Walter J. Balfour, Charles X.W. Qian and Chi Zhou, J. Chem. phys. 106, 4383 (1997); James F. Harrison, J. Phys. Chem. 100, 3513 (1996); Margareta R.A. Blomberg and Per E.M. Siegbahn, Theor. Chim. Acta. 81, 365 (1992).
Author Institution: Department of Chemistry and Biochemistry, Arizona State University

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