Resolving vibrational and structural contributions to isothermal compressibility

Stillinger, Frank H. ; Debenedetti, Pablo G. ; Sastry, Srikanth (1998) Resolving vibrational and structural contributions to isothermal compressibility Journal of Chemical Physics, 109 (10). pp. 3983-3988. ISSN 0021-9606

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Official URL: http://jcp.aip.org/resource/1/jcpsa6/v109/i10/p398...

Related URL: http://dx.doi.org/10.1063/1.476997

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.

Item Type:Article
Source:Copyright of this article belongs to American Institute of Physics.
Keywords:Compressibility; Vibrational States; Statistical Mechanics; Glass Transition; Supercooling; Vibrational Modes
ID Code:50154
Deposited On:21 Jul 2011 14:25
Last Modified:21 Jul 2011 14:25

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