METHYL ROTOR INDUCED IVR IN 2-PYRIDONE MEDIATED BY A DOUBLE HYDROGEN-BONDED CYCLIC INTERFACE

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2006

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Ohio State University

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Over the past three decades, many experimental and theoretical investigations have demonstrated that intramolecular vibrational energy redistribution (IVR) in an aromatic chromophore can be accelerated on substitution by a methyl group. In those studies the methyl group is attached directly to an aromatic site. In the present study, by measuring the laser-induced fluorescence spectra of 1:1 hydrogen-bonded mixed dimers of 2-pyridone (PY) with formic (FA), acetic (AA) and propanoic (PA) acids we demonstrate that the threshold of the excited state IVR is lowest in the case of PY$...$AA mixed dimer. We interpret the observation as due to coupling of the rotor mode of AA with the ring modes of 2-pyridone moiety mediated by the hydrogen bond modes of the cyclic dimeric interface. In the talk, the mechanism of such coupling will be discussed.

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Author Institution: Department of Chemistry, Indian Institute of Technology Kanpur, UP 208016, India; Department of Physical Chemistry, Indian Association for the Cultivation of Science,; Jadavpur, Calcutta 700032, India

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