Heavy-atom tunneling in cyclobutadiene:Ab initio calculation of the intensities ofa g Raman lines期刊界 All Journals 搜尽天下杂志传播学术成果专业期刊搜索期刊信息化学术搜索

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Heavy-atom tunneling in cyclobutadiene:Ab initio calculation of the intensities ofa g Raman lines

Authors:	P Čársky J Michl

Institution:	(1) J. Heyrovský Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences, 18223 Prague 8, Czechoslovakia;(2) Department of Chemistry and Biochemistry, University of Colorado at Boulder, 80309-0215 Boulder, CO, USA

Abstract:	Summary GVB/5s3p1d/3s1p] calculations were performed on the polarizability surface (₁, ₂, ₃) of cyclobutadiene. The threea _g coordinates refer to automerization (₁), symmetric CC stretch (₂), and symmetric CCH bend (₃). This surface was used together with the previously obtained variational vibrational wave functions for the calculation of Raman intensities. The calculation predicts comparable intensities for the two split components of the automerization Raman line in an isolated molecule and disagrees with observations on matrix-isolated cyclobutadiene. The disagreement is attributed to the asymmetry of the double-well potential imposed by the effect of the Ar matrix.Dedicated to Professor Ruedenberg

Keywords:	Raman intensities Tunneling Cyclobutadiene Ab initio calculations of polarizabilities Variational calculation of vibrational levels
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