Statistical mechanics of solvent induced forces and vibrational frequency shifts. Low density expansions and Monte Carlo simulations

Luís E S De Souza, Claudia B E Guerin, Dor Ben-Amotz, Igal Szleifer

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

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 languageEnglish (US)
Pages (from-to)9954-9961
Number of pages8
JournalThe Journal of Chemical Physics
Volume99
Issue number12
DOIs
StatePublished - 1993

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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