Anharmonic couplings underlying the ultrafast vibrational dynamics of hydrogen bonds in liquids

The multilevel structure and vibrational couplings of O-H stretching transitions in intermolecular hydrogen bonds of acetic acid dimers are determined by femtosecond two-dimensional photon-echo spectroscopy in the infrared. Combining experiment and theoretical calculations, we separate Fermi resonan...

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Published inPhysical review letters Vol. 95; no. 14; p. 147402
Main Authors Huse, N, Bruner, B D, Cowan, M L, Dreyer, J, Nibbering, E T J, Miller, R J D, Elsaesser, T
Format Journal Article
LanguageEnglish
Published United States 30.09.2005
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Summary:The multilevel structure and vibrational couplings of O-H stretching transitions in intermolecular hydrogen bonds of acetic acid dimers are determined by femtosecond two-dimensional photon-echo spectroscopy in the infrared. Combining experiment and theoretical calculations, we separate Fermi resonances with combination tones of fingerprint modes from anharmonic couplings to underdamped low-frequency modes of the dimer. A multilevel density matrix approach based on density functional theory calculations reproduces the experimental results and reveals coupling strengths of both mechanisms on the order of 40-150 cm(-1).
ISSN:0031-9007
DOI:10.1103/physrevlett.95.147402