Theoretical Two Dimensional Infrared Spectroscopy of Aqueous Solutions of tert -Butyl Alcohol: Variation of the Dynamics of Spectral Diffusion along the Percolation Transition.

Binary mixtures of water and tert -butyl alcohol (TBA) are known to exhibit the so-called percolation transition where small clusters of TBA molecules span into large aggregates beyond a threshold concentration of the alcohol. In the present study, we have investigated the linear and two-dimensional infrared spectral features of aqueous solutions of TBA for varying concentration of the alcohol along the percolation transition. The percolation transition is characterized through calculations of intermolecular radial distribution functions and average size of the largest cluster of TBA molecules. It is found that, with variation of alcohol concentration, the radial distribution functions of the central carbon atoms of TBA molecules show a nonmonotonic change in the height of the first peak and also the size of the largest cluster of TBA molecules show a jump in the increase of its size for TBA mole fraction between 0.04 and 0.06 corresponding to a transition from smaller clusters to larger spanning aggregates. However, it is found that the linear infrared spectrum of water does not exhibit any noticeable changes on variation of TBA concentration along the percolation transition. Subsequently, two-dimensional infrared (2DIR) spectra and vibrational frequency time correlation function of water are calculated for all the TBA-water solutions considered in this study. The spectral diffusion of water calculated from 2DIR is found to slow down with increase of the TBA concentration. The time scales of spectral diffusion of water, as characterized by the relaxation of frequency time correlation function, 2DIR metric of central line slope, and also the hydrogen bond time correlation functions, are found to exhibit a noticeable jump along the percolation transition. The hydrophilic group of TBA is found to retard the water dynamics more effectively than the hydrophobic groups. Also, the jump in the dynamical slowdown along the percolation transition is found to be more significant for water molecules at the hydrophilic sites.