TY - JOUR
T1 - Resolving vibrational and structural contributions to isothermal compressibility
AU - Stillinger, Frank H.
AU - Debenedetti, Pablo G.
AU - Sastry, Srikanth
N1 - Copyright:
Copyright 2005 Elsevier B.V., All rights reserved.
PY - 1998
Y1 - 1998
N2 - 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.
AB - 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.
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U2 - 10.1063/1.476997
DO - 10.1063/1.476997
M3 - Article
AN - SCOPUS:0000983399
VL - 109
SP - 3983
EP - 3988
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 10
ER -