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Layerwise decomposition of water dynamics in reverse micelles: A simulation study of two-dimensional infrared spectrum

Biswas, Rajib and Furtado, Jonathan and Bagchi, Biman (2013) Layerwise decomposition of water dynamics in reverse micelles: A simulation study of two-dimensional infrared spectrum. In: JOURNAL OF CHEMICAL PHYSICS, 139 (14).

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Official URL: http://dx.doi.org/10.1063/1.4824446


We present computer simulation study of two-dimensional infrared spectroscopy (2D-IR) of water confined in reverse micelles (RMs) of various sizes. The present study is motivated by the need to understand the altered dynamics of confined water by performing layerwise decomposition of water, with an aim to quantify the relative contributions of different layers water molecules to the calculated 2D-IR spectrum. The 0-1 transition spectra clearly show substantial elongation, due to in-homogeneous broadening and incomplete spectral diffusion, along the diagonal in the surface water layer of different sized RMs. Fitting of the frequency fluctuation correlation functions reveal that the motion of the surface water molecules is sub-diffusive and indicate the constrained nature of their dynamics. This is further supported by two peak nature of the angular analogue of van Hove correlation function. With increasing system size, the water molecules become more diffusive in nature and spectral diffusion almost completes in the central layer of the larger size RMs. Comparisons between experiments and simulations establish the correspondence between the spectral decomposition available in experiments with the spatial decomposition available in simulations. Simulations also allow a quantitative exploration of the relative role of water, sodium ions, and sulfonate head groups in vibrational dephasing. Interestingly, the negative cross correlation between force on oxygen and hydrogen of O-H bond in bulk water significantly decreases in the surface layer of each RM. This negative cross correlation gradually increases in the central water pool with increasing RMs size and this is found to be partly responsible for the faster relaxation rate of water in the central pool. (C) 2013 AIP Publishing LLC.

Item Type: Journal Article
Additional Information: copyright for this article belongs to AIP
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited: 26 Nov 2013 15:18
Last Modified: 26 Nov 2013 15:18
URI: http://eprints.iisc.ac.in/id/eprint/47790

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