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- W2081892685 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, is consistent with enhanced C−H and O−H hydrogen-bond formation at high pressure (even in nonpolar solvents). Systems studied include n-butanol, acetone, chloroform-d, ethane, and methyl iodide in the pure liquid state or dissolved in carbon disulfide, n-propyl bromide, n-propyl iodide, toluene, 2,3-dimethylbutane, methanol, tetrahydrofuran, or methylene chloride." @default.
- W2081892685 created "2016-06-24" @default.
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- W2081892685 date "2000-07-26" @default.
- W2081892685 modified "2023-10-17" @default.
- W2081892685 title "Intermolecular Forces and Bond Length Changes in High-Pressure Fluids. Vibrational Spectroscopic Measurement and Generalized Perturbed Hard Fluid Analysis" @default.
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- W2081892685 doi "https://doi.org/10.1021/jp0016479" @default.
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