American Institute of Physics, The Journal of Chemical Physics, 1(119), p. 423-434, 2003
DOI: 10.1063/1.1578058
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Frequency resolved pump-probe experiments have been conducted on the deuterated hydroxyl stretch of methanol-d in a solution containing 0.8% methanol-d/23% methanol-h in carbon tetrachloride. Methanol-d molecules that both donate and receive hydrogen bonds have an inhomogeneously broadened hydroxyl stretch absorption line centered at 2487 cm−1. With a laser tuned to 2513 cm−1, the high-frequency side of the absorption spectrum is excited. The equilibration of the excited state peak and the ground-state hole results in the time-dependent shift in the frequency of the signal, which is used to monitor the dynamics of spectral diffusion. Model calculations were conducted to address the influence of spectral diffusion in the ground and excited states on the experimental observables when the vibrational lifetime is comparable to the spectral diffusion time. The model calculations illustrate the influence on the signal of absorbers in the ground state that have relaxed from the excited state. This aspect of the problem has not been addressed in previous descriptions of frequency resolved pump-probe spectroscopy. The calculations were used to fit the time-dependent peak maximum, resulting in a bi-exponential frequency–frequency correlation function, with a fast time constant of roughly 0.1 ps and a slower time constant of 1.6±0.3 ps. The observed dynamics have been compared with the predictions of dielectric continuum theory. The inability of a simple dielectric continuum theory to predict the observed spectral diffusion dynamics suggests that these dynamics do not result from the long-wavelength, collective orientational relaxation of the solvent. Instead the dynamics are attributed to fluctuations in the local hydrogen bond network, which is consistent with recent molecular-dynamics simulations of vibrational transient hole burning in water. © 2003 American Institute of Physics.