Basic requirements for potential differences across solid--fluid interfaces

TL;DR

This study uses molecular dynamics simulations to identify the molecular features that cause potential differences at solid-fluid interfaces, emphasizing the roles of molecular asymmetry and dipole positioning.

Contribution

It establishes a criterion that molecular asymmetry and off-center dipoles are necessary for surface potentials to develop at solid-fluid interfaces.

Findings

Charge oscillations occur only with asymmetric molecules or off-center dipoles.

Solid-fluid interaction strength influences charge oscillations but not the surface potential magnitude.

Changing atomic sizes can reverse the sign of the surface potential.

Abstract

At model water--vapor and water--solid interfaces, molecular ordering leads to charge oscillations and, thereby, to a spatially varying electrostatic potential. Atomistic simulations indicate that such ordering leads to an electric potential difference $\chi$, the surface potential, of about $-0.5\,\mathrm{V}$ across the first few molecular layers. Here, we calculate surface potentials at interfaces between a simple model fluids and a solid, with Molecular Dynamics simulations. The fluids are made up of either diatomic, dipolar molecules or a single Lennard-Jones particle with a dipole moment. All fluids show some structuring near the interface, but charge oscillations and a non-zero surface potential are present only for asymmetric molecules (unequal diameters of the atoms) or molecules with an off-center dipole. We condense this finding into the criterion that the geometric and dipolar centers of a molecule must differ for the fluid to exhibit a surface potential. Remarkably, while the solid--fluid interaction strength strongly affects the magnitude of charge oscillations, it hardly affects the potential drop $\chi$. Further, our results demonstrate that changing the diameter of the smaller atom can flip the sign of the surface potential, thus highlighting the importance of steric effects.