Show simple item record

dc.creatorFinnigan, David J.en_US
dc.creatorCox, A. Peteren_US
dc.creatorWhittle, John M.en_US
dc.date.accessioned2006-06-15T13:30:39Z
dc.date.available2006-06-15T13:30:39Z
dc.date.issued1972en_US
dc.identifier1972-E-8en_US
dc.identifier.urihttp://hdl.handle.net/1811/8974
dc.descriptionPresent 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.descriptionAuthor Institution: School of Chemistry, The Universityen_US
dc.description.abstractAn 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.extent195436 bytes
dc.format.mimetypeimage/jpeg
dc.language.isoEnglishen_US
dc.publisherOhio State Universityen_US
dc.titleANALYSIS OF $v_{t} = 1$ AND HIGHER DEGENERATE EXCITED STATES IN THE MICROWAVE SPECTRA OF $C_{5v}$ AND $C_{3v}$ MOLECULESen_US
dc.typearticleen_US


Files in this item

Thumbnail

Items in Knowledge Bank are protected by copyright, with all rights reserved, unless otherwise indicated.

This item appears in the following Collection(s)

Show simple item record