Computational study of the signature of hydrogen-bond strength on the infrared spectra of a hydrogen-bonded complex dissolved in a polar liquid

Chemical Physics 370

Abstract
The signature of hydrogen-bond strength on the one- and two-dimensional infrared spectra of the hydrogen-stretch in a hydrogen-bonded complex dissolved in a polar liquid was investigated via mixed quantum–classical molecular dynamics simulations. Non-Condon effects were found to intensify with increasing hydrogen-bond strength and to shift oscillator strength from the stable configurations that correspond to the ionic and covalent tautomers into unstable configurations that correspond to the transition-state between them. The transition-state peak is observed to blue shift and increase in intensity with increasing hydrogen-bond strength, and to dominate the spectra in the case of a strong hydrogen-bond. It is argued that the application of multidimensional infrared spectroscopy in the region of the transition-state peak can provide a uniquely direct probe of the molecular events underlying breaking and forming of hydrogen-bonds in the condensed phase.

Chemical Physics 370, 201-207 (2010) doi: 10.1016/j.chemphys.2010.01.013

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