Neural-Network Assisted Study of Nitrogen Atom Dynamics on Amorphous Solid Water -- II. Diffusion

TL;DR

This study combines machine learning, metadynamics, and kinetic Monte Carlo simulations to accurately compute nitrogen atom diffusion on amorphous solid water, revealing extremely low diffusion rates at 10 K and the significant influence of surface coverage.

Contribution

It introduces a novel computational approach to determine diffusion coefficients of atoms on amorphous ice, highlighting the impact of surface conditions and challenging previous assumptions about diffusion barriers.

Findings

Nitrogen atoms have negligible diffusion on bare amorphous water ice at 10 K.

Surface coverage can enhance diffusion by 9-12 orders of magnitude.

Atom tunneling has minimal effect on diffusion at low temperatures.

Abstract

The diffusion of atoms and radicals on interstellar dust grains is a fundamental ingredient for predicting accurate molecular abundances in astronomical environments. Quantitative values of diffusivity and diffusion barriers usually rely heavily on empirical rules. In this paper, we compute the diffusion coefficients of adsorbed nitrogen atoms by combining machine-learned interatomic potentials, metadynamics, and kinetic Monte Carlo simulations. With this approach, we obtain a diffusion coefficient of nitrogen atoms on the surface of amorphous solid water of merely $(3.5 \pm 1.1)10^{-34}$cm$^2$s$^{-1}$ at 10 K for a bare ice surface. Thus, we find that nitrogen, as a paradigmatic case for light and weakly bound adsorbates, is unable to diffuse on bare amorphous solid water at 10 K. Surface coverage has a strong effect on the diffusion coefficient by modulating its value over 9--12 orders of magnitude at 10 K and enables diffusion for specific conditions. In addition, we have found that atom tunneling has a negligible effect. Average diffusion barriers of the potential energy surface (2.56 kJ mol$^{-1}$) differ strongly from the effective diffusion barrier obtained from the diffusion coefficient for a bare surface (6.06 kJ mol$^{-1}$) and are, thus, inappropriate for diffusion modeling. Our findings suggest that the thermal diffusion of N on water ice is a process that is highly dependent on the physical conditions of the ice.