Insights into the Structure of Cyclohexane from Femtosecond Degenerate Four-Wave Mixing Spectroscopy and Ab Initio Calculations

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• 作者：Christoph Riehn ; Victor V. Matylitsky ; W//pubs.acs.org/images/entities/lstrok.gif" border="0">odzimierz Jarz//pubs.acs.org/images/entities/ecedil.gif" border="0">ba ; Bern
• 刊名：Journal of the American Chemical Society
• 出版年：2003
• 出版时间：December 31, 2003
• 年：2003
• 卷：125
• 期：52
• 页码：16455 - 16462
• 全文大小：108K
• 年卷期：v.125,no.52(December 31, 2003)
• ISSN：1520-5126

文摘

In this paper, we report the use of femtosecond time-resolved degenerate four-wave mixingrotationally resolved spectroscopy to obtain very accurate structural information on the symmetric topcyclohexane. Apart from highlighting the versatility of this method in determining accurate structures oflarge and complex molecules without dipole moment, the present study also details the comparison of theexperimentally determined rotational constant B₀ with that obtained from high-level ab initio calculations.The theoretical calculations, which were carried out at both the second-order Mller-Plesset (MP2) andcoupled-cluster with single, double, and perturbative triple substitutions [CCSD(T)] levels of theory, alsotake into account vibrational averaging effects. A detailed investigation of the vibrational averaging effectsreveals that the corrections emerge from only the six highly symmetric A_1g modes, a justification of whichis provided by an analysis of these modes.