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Updated: Jul 30, 2025

An Analog Macroscopic Technique for Studying Molecular Hydrodynamic Processes in Dense Gases and Liquids
Published on: December 4, 2017
Frequency-dependent hydrodynamic finite size correction in molecular simulations reveals the long-time hydrodynamic
Laura Scalfi1, Domenico Vitali1, Henrik Kiefer1
1Fachbereich Physik, Freie Universität Berlin, Arnimallee 14, 14195 Berlin, Germany.
Abstract:
Finite-size effects are challenging in molecular dynamics simulations because they have significant effects on computed static and dynamic properties, in particular diffusion constants, friction coefficients, and time- or frequency-dependent response functions. We investigate the influence of periodic boundary conditions on the velocity autocorrelation function and the frequency-dependent friction of a particle in a fluid, and show that the long-time behavior (starting at the picosecond timescale) is significantly affected. We develop an analytical correction allowing us to subtract the periodic boundary condition effects. By this, we unmask the power-law long-time tails of the memory kernel and the velocity autocorrelation function in liquid water and a Lennard-Jones fluid from simulations with rather small box sizes.
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