Non-equilibrium simulations of thermally induced electric fields in water

TL;DR

This study uses non-equilibrium molecular dynamics to explore how different treatments of long-range interactions affect thermally induced electric fields in water, revealing significant discrepancies and proposing improved calculation methods.

Contribution

It demonstrates the impact of electrostatic treatment methods on simulated electric fields and molecular orientations, introducing a more accurate calculation approach.

Findings

Wolf method underestimates field strength compared to Ewald summation.

Incorrect kernel use leads to wrong molecular orientation predictions.

Analytical averaging reduces error bars and simulation time.

Abstract

Using non-equilibrium molecular dynamics simulations, it has been recently demonstrated that water molecules align in response to an imposed temperature gradient, resulting in an effective electric field. Here, we investigate how thermally induced fields depend on the underlying treatment of long-ranged interactions. For the short-ranged Wolf method and Ewald summation, we find the peak strength of the field to range between $2 \times 10^7$ and $5 \times 10^7~\text{V/m}$ for a temperature gradient of $5.2~\text{K/}\unicode{x212B}$. Our value for the Wolf method is therefore an order of magnitude lower than the literature value [J. Chem. Phys. 139, 014504 (2013) and 143, 036101 (2015)]. We show that this discrepancy can be traced back to the use of an incorrect kernel in the calculation of the electrostatic field. More seriously, we find that the Wolf method fails to predict correct molecular orientations, resulting in dipole densities with opposite sign to those computed using Ewald summation. By considering two different multipole expansions, we show that, for inhomogeneous polarisations, the quadrupole contribution can be significant and even outweigh the dipole contribution to the field. Finally, we propose a more accurate way of calculating the electrostatic potential and the field. In particular, we show that averaging the microscopic field analytically to obtain the macroscopic Maxwell field reduces the error bars by up to an order of magnitude. As a consequence, the simulation times required to reach a given statistical accuracy decrease by up to two orders of magnitude.