Issue 11, 2022

Equilibrium distribution functions: connection with microscopic dynamics

Abstract

Standard textbook derivations of the equilibrium distribution function rely on assumptions that may not satisfy all readers. Here, we present a straightforward approach to derive the equilibrium distribution function from the microscopic dynamics, and review how it can be used to obtain the expected expressions. In molecular dynamics simulations the equations of motion are often modified to simulate different ensembles or phenomena. We show that in some cases these equations will sample an equilibrium ensemble whereas in other cases they will not. For example, we find that for charged particles driven by a field, an equilibrium distribution is only possible when the system is confined. Furthermore, the approach correctly predicts that neither SLLOD shear flow dynamics nor constant temperature dynamics with a Berendsen thermostat sample any time-independent phase space distributions.

Graphical abstract: Equilibrium distribution functions: connection with microscopic dynamics

Supplementary files

Article information

Article type
Perspective
Submitted
20 Nov. 2021
Accepted
25 Febr. 2022
First published
28 Febr. 2022

Phys. Chem. Chem. Phys., 2022,24, 6383-6392

Equilibrium distribution functions: connection with microscopic dynamics

C. F. Petersen and D. J. Searles, Phys. Chem. Chem. Phys., 2022, 24, 6383 DOI: 10.1039/D1CP05316G

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