Nanoclustering in non-ideal ethanol/heptane solutions alters solvation dynamics.

Abstract

Alcohol/alkane solutions widely used in chemical synthesis and as transportation fuels are highly non-ideal due to the nanoscale clustering of the amphiphilic alcohol molecules within the nonpolar alkanes. Besides impacting reactivity, such as combustion, non-ideal solutions are likely to exhibit unusual solvation dynamics on ultrafast time scales arising from the structurally heterogeneous nature of molecular-scale association. Using a convenient transition metal carbonyl vibrational probe [(C5H5)Mn(CO)3, CMT], linear absorption and nonlinear two-dimensional infrared (2D-IR) spectroscopy reveal composition-dependent solvation dynamics as reported by the frequency fluctuation correlation function in a series of ethanol/heptane solutions. Slow spectral diffusion with dilute ethanol indicates preferential solvation of the polar solute by the alcohol with a mechanism largely dominated by solvent exchange. Comparison with an ethanol/acetonitrile solution series yields no substantial preferential solvation or solvent exchange signatures in the linear or 2D-IR spectra. In ethanol/heptane solutions, increasing the ethanol concentration speeds up the solvation dynamics, which is largely consistent with a model that includes solvent exchange and single-solvent spectral diffusion. Detailed analysis of the deviation from the experimental time constants from the model's optimal parameters yields a remarkable resemblance of the concentration-weighted Kirkwood-Buff integrals for ethanol/heptane solutions. This trend indicates that solution non-ideality alters the spectral diffusion dynamics of the probe solute. Given that nanoscale clustering drives the non-ideality, these experiments reveal a dynamical consequence of nanoscale heterogeneity on the ultrafast dynamics of the solution. Refined understanding of the structural and dynamical aspects of mixed solvents will be necessary for predictive solution strategies in chemistry.