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Frequency-dependent hydrodynamic finite size correction in molecular simulations reveals the long-time hydrodynamic tail

L. Scalfi, D. Vitali, H. Kiefer, R. R. Netz – 2023

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.

Title
Frequency-dependent hydrodynamic finite size correction in molecular simulations reveals the long-time hydrodynamic tail
Author
L. Scalfi, D. Vitali, H. Kiefer, R. R. Netz
Date
2023
Identifier
DOI: 10.1063/5.0151406
Source(s)
Citation
J. Chem. Phys. 2023, 158, 191101
Type
Text