Molecular Structure, Vinyl Rotation Barrier, and Vibrational Dynamics of 2,6-Dichlorostyrene. A Theoretical and Experimental Research

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• 作者：Antonio A. Ceacero-Vega ; Tomá ; s Peñ ; a Ruiz ; Manuel Ferná ; ndez Gó ; mez ; José ; M. Granadino Roldá ; n ; Amparo Navarro ; M. Paz Ferná ; ndez-Liencres ; Upali A. Jayasoor
• 刊名：Journal of Physical Chemistry A
• 出版年：2007
• 出版时间：July 19, 2007
• 年：2007
• 卷：111
• 期：28
• 页码：6406 - 6419
• 全文大小：345K
• 年卷期：v.111,no.28(July 19, 2007)
• ISSN：1520-5215

文摘

The molecular structure of 2,6-dichlorostyrene has been analyzed at MP2 and DFT levels using differentbasis sets concluding in a nonplanar geometry. The influence of either the level of theory or the nature of thesubstituent has been assessed. The vinyl-phenyl torsion barrier has also been investigated as a function oflevel of theory. The ultimate factors responsible for the torsion barrier have been studied using two differentpartitioning schemes, i.e., the total electronic potential energy and the natural bond orbital, NBO. A topologicalanalysis of the electron density within the atom-in-molecule, AIM, theory predicts soft intramolecular chlorine(ring)-hydrogen (vinyl) contacts when the system becomes planar. A first complete vibrational study hasbeen performed using theoretical data and experimental vibrational frequencies from IR, Raman and, for thefirst time, inelastic neutron scattering, INS, spectra. The new assignment proposed is based on a scaled quantummechanical, SQM, force field and the wavenumber linear scaling, WLS, approach.