Long-timescale simulations of H$_2$O admolecule diffusion on Ice Ih(0001) surfaces

TL;DR

This study uses long-timescale simulations to analyze H$_2$O admolecule diffusion on ice Ih surfaces, revealing how surface structure and temperature influence diffusion rates and energy landscapes.

Contribution

It provides detailed insights into water molecule diffusion on ice surfaces, highlighting differences between disordered and ordered (Fletcher) surfaces using advanced simulation techniques.

Findings

Diffusion constants align with experimental upper bounds.

Dangling H atoms rearrange to reduce clustering.

Ordered Fletcher surfaces facilitate faster diffusion.

Abstract

Long-timescale simulations of the diffusion of a H$_2$O admolecule on the (0001) basal plane of ice Ih were carried out over a temperature range of 100 to 200 K using the adaptive kinetic Monte Carlo method and TIP4P/2005f interaction potential function. The arrangement of dangling H atoms was varied from the proton-disordered surface to the perfectly ordered Fletcher surface. A large variety of sites was found leading to a broad distribution in adsorption energy at both types of surfaces. Up to 4 % of the sites on the proton-disordered surface have an adsorption energy exceeding the cohesive energy of ice Ih. The mean squared displacement of a simulated trajectory at 175 K for the proton-disordered surface gave a diffusion constant of 6$\cdot$10$^{-10}$ cm$^2$/s, consistent with an upper bound previously reported from experimental measurements. During the simulation, dangling H atoms were found to rearrange so as to reduce clustering, thereby approaching a linear Fletcher type arrangement. Diffusion on the perfectly ordered Fletcher surface was estimated to be significantly faster, especially in the direction along the rows of dangling hydrogen atoms. From simulations over the range in temperature, an effective activation energy of diffusion was estimated to be 0.16 eV and 0.22 eV for diffusion parallel and perpendicular to the rows, respectively. Even a slight disruption of the rows of the Fletcher surface made the diffusion isotropic.