Time-resolved multidimensional infrared spectroscopy of the hydroxyl stretch is a uniquely detailed probe of hydrogen bond structure and dynamics. The relatively strong coupling with the environment gives rise to a dynamical Stokes shift that report on <i>nonequilibrium</i> solvation processes, rather than on <i>equilibrium</i> frequency fluctuations. Furthermore, the energy released during population relaxation can lead to breaking of hydrogen bonds, thereby extending the signal lifetime beyond the excited state lifetime. We present a general mixed quantum-classical methodology for modeling spectra that can account for such effects, and use it to obtain a molecular interpretation of recently measured pump-probe infrared spectra of methanol/carbon-tetrachloride liquid mixtures and syn/anti tetrols dissolved in liquid chloroform.

Time-resolved infrared spectroscopy as a probe of nonequilibrium hydrogen-bond dynamics: A mixed quantum-classical study of alcohols in liquid solution

253rd National Meeting (2017)

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