Abstract
Theoretical expressions are presented for the solvent configuration averaged force on a diatomic solute throughout the vapor-liquid density range. Analytical low density expansions and solvent configurational space averages are used to predict solvent induced changes in solute vibrational frequency. Purely classical Monte Carlo simulation results for a system representing bromine (Br2) dissolved in argon agree quantitatively with previous coupled quantum-classical results of Herman and Berne, up to liquid densities. It is found to be impossible to obtain a red gas to liquid shift (such as that typically observed experimentally) in any realistic diatomic system with only binary solvent atom-solute atom interaction potentials. However, redshifts are predicted when a three-atom potential, in which the solute-solvent interaction depends on solute bond length, is introduced.
Original language | English (US) |
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Pages (from-to) | 9954-9961 |
Number of pages | 8 |
Journal | The Journal of Chemical Physics |
Volume | 99 |
Issue number | 12 |
DOIs | |
State | Published - 1993 |
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry