Resolving vibrational and structural contributions to isothermal compressibility

Frank H. Stillinger, Pablo G. Debenedetti, Srikanth Sastry

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

The well-known and general "compressibility theorem" for pure substances relates κT =-(∂lnV/∂p)N,T to a spatial integral involving the pair correlation function g(2). The isochoric inherent structure formalism for condensed phases separates g(2) into two fundamentally distinct contributions: a generally anharmonic vibrational part, and a structural relaxation part. Only the former determines κT for low-temperature crystals, but both operate in the liquid phase. As a supercooled liquid passes downward in temperature through a glass transition, the structural contribution to κT switches off to produce the experimentally familiar drop in this quantity. The Kirkwood-Buff solution theory forms the starting point for extension to mixtures, with electroneutrality conditions creating simplifications in the case of ionic systems.

Original languageEnglish (US)
Pages (from-to)3983-3988
Number of pages6
JournalJournal of Chemical Physics
Volume109
Issue number10
DOIs
StatePublished - 1998

All Science Journal Classification (ASJC) codes

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

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