On the accurate calculation of the dielectric constant and the diffusion coefficient from molecular dynamics simulations: the case of SPC/E water

TL;DR

This study investigates how trajectory length, system size, and potential models affect the accuracy of calculating dielectric constant and diffusion coefficient in molecular dynamics simulations of SPC/E water, emphasizing the need for long simulations.

Contribution

It provides a detailed analysis of the convergence behavior of dielectric and diffusion properties, highlighting the importance of long trajectories and system size considerations for accurate results.

Findings

Trajectories shorter than 6 ns are insufficient for accurate dielectric constant estimation.

Radial distribution functions are insensitive to system size.

Dielectric constant and diffusion coefficient are sensitive to trajectory length and system size.

Abstract

The effect of the applied trajectory length on the convergence of the static dielectric constant and the self-diffusion coefficient were examined for the SPC/E water model in the NVT ensemble with different system size at 293 K. Very long simulation times of 6-8 ns were employed in order to track the convergence of these properties. Temperature dependence and isotope effects, via using D$_2$O instead of H$_2$O, were also investigated. A simulation for the polarizable SWM4-DP model was also carried out to compare the effect of different potential models. Radial distribution functions and the neutron weighted structure factor were also calculated; they were found to be insensitive to changing the system size in the range of 216-16000 molecules. On the other hand, the static dielectric constant and the diffusion coefficient are rather sensitive to the applied trajectory length, system size and the method of calculation. These latter properties are therefore not appropriate for assessing, and distinguishing between, potential models of water. It is clearly shown that trajectories shorter than about 6 ns are not sufficient for a sufficiently accurate determination of the dielectric constant of this water model.