Geometry determination of complexes in a molecular liquid mixture using electron–vibration–vibration two-dimensional infrared spectroscopy with a vibrational transition density cube method

文献情報

出版日 2012-09-06

DOI 10.1039/C2CP42593A

インパクトファクター 3.676

著者

Rui Guo, Shaul Mukamel, David R. Klug

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要旨

We demonstrate the use of a new vibrational transition density cube (VTDC) method for determining the geometry of complexes in a molecular liquid mixture from electron–vibration–vibration two-dimensional infrared (EVV 2DIR) spectra. The VTDC method was used to calculate the electrically-mediated intermolecular vibrational coupling and thereby the EVV 2DIR spectra. Using the 1 : 1 benzonitrile–phenylacetylene (BN–PA) liquid mixture as a test case, the new method leads to a distance of 3.60 Å between the interacting BN–PA pair, a much more accurate value than the distance previously obtained using a dipolar approximation for the electrical coupling. We also show that molecular dynamics simulations of the liquid mixture predict a modal geometry of complexation which agrees well with the geometry determined from the 2DIR data via VTDC analysis. We therefore conclude the combination of VTDC and EVV 2DIR data is a useful approach for the determination of the geometry of molecular complexes in the condensed phase.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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