dc.creator Finnigan, David J. en_US dc.creator Cox, A. Peter en_US dc.creator Whittle, John M. en_US dc.date.accessioned 2006-06-15T13:30:39Z dc.date.available 2006-06-15T13:30:39Z dc.date.issued 1972 en_US dc.identifier 1972-E-8 en_US dc.identifier.uri http://hdl.handle.net/1811/8974 dc.description Present address of David J. Finnigan: Dept. of Chemistry, Harvard University, Cambridge, Mass. 02138 $^{1}$ A.P. Cox, A.H. Brittain and M. J. Whittle, J. Mol. Spectr., 35, 49 (1970). $^{2}$ M. L. Grenier-Besson and G. Amat, J. Mol. Spectr., 8, 22 (1962)."" en_US dc.description Author Institution: School of Chemistry, The University en_US dc.description.abstract An analysis of the microwave spectrum of the $C_{5v}$ molecule $C_{5}H_{5}NiNO$ in the first excited state, $v_{14} = 1$, of the lowest $E_{1}$ vibration has been $reported.^{1}$ A perturbation formula was used, analogous to that derived by Grenier-Besson and $Amat^{2}$ for $C_{3v}$ molecules. The present communication by describes the analysis of higher excited states, $v_{14} = {2,3}$ and 4, where perturbation techniques are inadequate due to strong accidental $\ell$-type resonances. Considering only the $\langle\ell,K|h^{\prime}_{2}|\ell\pm2,K\pm2\rangle$ off-diagonal elements, the energy matrices can be factorized into submatrices of maximum order $(v+1)$. This factorization facilitates the diagonalization of the energy matrices and hence computation of the microwave frequencies. The usual vibration-rotation constants have been determined by a non-linear least squares treatment together with the anharmonic constant, $x_{\ell_{t} \ell_{t}}$ associated with $\ell$-type resonance for$\ v > 1$. For $C_{3v}$ molecules in the absence of r-type resonances involving the $\langle 2,-1 \rangle$ elements the same factorization is proposed. This enables the analytical procedure outlined above to be applied, thus accounting accurately for $\ell$-type resonance where perturbation methods prove inadequate. This treatment facilitates the analysis of higher excited states, but is often required for $v_{t} = 1$ when ${_{q}}[J(J+1)]/2\sim|B-A+A\xi|$. Such is the case for $CF_{3}CN$ and an analysis for $v_{8} = 1$ and 2 will be reported. en_US dc.format.extent 195436 bytes dc.format.mimetype image/jpeg dc.language.iso English en_US dc.publisher Ohio State University en_US dc.title ANALYSIS OF $v_{t} = 1$ AND HIGHER DEGENERATE EXCITED STATES IN THE MICROWAVE SPECTRA OF $C_{5v}$ AND $C_{3v}$ MOLECULES en_US dc.type article en_US
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