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 - Jan 1 1993

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'Statistical mechanics of solvent induced forces and vibrational frequency shifts. Low density expansions and Monte Carlo simulations'. Together they form a unique fingerprint.

Cite this