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Solvation dynamics in monohydroxy alcohols: Agreement between theory and different experiments

Biswas, R and Nandi, N and Bagchi, B (1997) Solvation dynamics in monohydroxy alcohols: Agreement between theory and different experiments. In: Journal of Physical Chemistry B, 101 (15). pp. 2968-2979.

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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/chin.19...


Recently three different experimental studies on ultrafast solvation dynamics in monohydroxy straight-chain alcohols (C-1-C-4) have been carried out, with an aim to quantify the time constant (and the amplitude) of the ultrafast component. The results reported are, however, rather different from different experiments. In order to understand the reason for these differences, we have carried out a detailed theoretical study to investigate the time dependent progress of solvation of both an ionic and a dipolar solute probe in these alcohols. For methanol, the agreement between the theoretical predictions and the experimental results [Bingemann and Ernsting J. Chem. Phys. 1995, 102, 2691 and Horng et al. J: Phys, Chern, 1995, 99, 17311] is excellent. For ethanol, propanol, and butanol, we find no ultrafast component of the time constant of 70 fs or so. For these three liquids, the theoretical results are in almost complete agreement with the experimental results of Horng et al. For ethanol and propanol, the theoretical prediction for ionic solvation is not significantly different from that of dipolar solvation. Thus, the theory suggests that the experiments of Bingemann and Ernsting and those of Horng et al. studied essentially the polar solvation dynamics. The theoretical studies also suggest that the experimental investigations of Joo et al. which report a much faster and larger ultrafast component in the same series of solvents (J. Chem. Phys. 1996, 104, 6089) might have been more sensitive to the nonpolar part of solvation dynamics than the polar part. In addition, a discussion on the validity of the present theoretical approach is presented. In this theory the ultrafast component arises from almost frictionless inertial motion of the individual solvent molecules in the force field of its neighbors.

Item Type: Journal Article
Publication: Journal of Physical Chemistry B
Publisher: American Chemical Society
Additional Information: Copyright of this article belongs to American Chemical Society.
Keywords: phase equilibria;interface equilibria;association equilibria;other natural products
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited: 03 Aug 2011 10:27
Last Modified: 03 Aug 2011 10:27
URI: http://eprints.iisc.ac.in/id/eprint/38458

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