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Temperature dependence of the two-dimensional infrared spectrum of liquid H2O.


ABSTRACT: Two-dimensional infrared photon-echo measurements of the OH stretching vibration in liquid H2O are performed at various temperatures. Spectral diffusion and resonant energy transfer occur on a time scale much shorter than the average hydrogen bond lifetime of approximately 1 ps. Room temperature measurements show a loss of frequency and, thus, structural correlations on a 50-fs time scale. Weakly hydrogen-bonded OH stretching oscillators absorbing at high frequencies undergo slower spectral diffusion than strongly bonded oscillators. In the temperature range from 340 to 274 K, the loss in memory slows down with decreasing temperature. At 274 K, frequency correlations in the OH stretch vibration persist beyond approximately 200 fs, pointing to a reduction in dephasing by librational excitat

SUBMITTER: Kraemer D 

PROVIDER: S-EPMC2206554 | biostudies-literature | 2008 Jan

REPOSITORIES: biostudies-literature