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Title: A Maxwell relation for dynamical timescales with application to the pressure and temperature dependence of water self-diffusion and shear viscosity
A Maxwell relation for a reaction rate constant (or other dynamical timescale) obtained under constant pressure, p , and temperature, T , is introduced and discussed. Examination of this relationship in the context of fluctuation theory provides insight into the p and T dependence of the timescale and the underlying molecular origins. This Maxwell relation motivates a suggestion for the general form of the timescale as a function of pressure and temperature. This is illustrated by accurately fitting simulation results and existing experimental data on the self-diffusion coefficient and shear viscosity of liquid water. A key advantage of this approach is that each fitting parameter is physically meaningful.  more » « less
Award ID(s):
2102656 1800559 2117449
NSF-PAR ID:
10414567
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Physical Chemistry Chemical Physics
Volume:
25
Issue:
18
ISSN:
1463-9076
Page Range / eLocation ID:
12820 to 12832
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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