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Elsevier, Chemical Physics Letters, 3-4(374), p. 362-371

DOI: 10.1016/s0009-2614(03)00643-2

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Ultrafast heterodyne detected infrared multidimensional vibrational stimulated echo studies of hydrogen bond dynamics

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This paper is available in a repository.

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Abstract

Multidimensional vibrational stimulated echo correlation spectra with full phase information are presented for the broad hydroxyl stretch band of methanol-OD oligomers in CCl4 using ultrashort (<50 fs) infrared pulses. Hydrogen bond breaking permits data to be acquired for times much greater than the vibrational lifetime. The data indicates that vibrational relaxation leads to preferential hydrogen bond breaking for oligomers on the red side of the spectrum. An off diagonal peak in the correlation spectrum that appears at long time (>1 ps) shows that there is frequency correlation between the initially excited hydroxyl stretch and the frequency shifted hydroxyl stretch formed by hydrogen bond breaking.