Abstract
Pressure-dependent vibrational frequency shifts are used to measure intermolecular-interaction-induced forces and bond length changes in solution. The results are employed to quantitate changes in solute−solvent coupling as a function of solvent density using a generalized perturbed hard fluid (G-PHF) analysis of solvent mean-force-induced perturbations of molecular potential energy surfaces. Repulsive solvation forces are calculated using the cavity distribution function of a reference hard-sphere fluid. Attractive forces are treated using a generalized van der Waals mean-field approximation, which allows for both long-range and short-range solute−solvent cohesive interactions. The results indicate marked differences in the density dependence of the attractive solvation force along different types of bonds. Hydrogen stretch vibrations (i.e., C−H and O−H stretches) display a strongly nonlinear density dependence, which is indicative of a short-range attractive solute−solvent coupling mechanism and, thus, ...
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