CO Diffusion on Interstellar Amorphous Solid Water: A Computational Study

TL;DR

This study models the diffusion of CO on amorphous water ice surfaces using quantum-chemical methods, revealing a wide distribution of diffusion energies that impact astrochemical processes and suggesting revisions to key model parameters.

Contribution

It provides the first detailed quantum-chemical analysis of CO diffusion on amorphous solid water, highlighting surface heterogeneity and its effects on astrochemical modeling.

Findings

Diffusion energy barriers vary widely due to surface heterogeneity.

Surface mobility influences CO desorption and reactivity.

Key astrochemical parameters need revision based on results.

Abstract

Surface chemistry on interstellar dust grains is recognized as a central component in astrochemical models, representing a plausible formation route for many of the observed complex molecular species. However, key parameters governing interstellar surface chemistry, such as diffusion energy barriers, remain poorly constrained. In particular, surface diffusion constitutes a fundamental step for the synthesis of complex organic molecules and plays a crucial role in understanding the desorption process. In this paper, the diffusion dynamics of carbon monoxide (CO) on amorphous solid water (ASW) surfaces, representative of interstellar ices, is modeled with quantum-chemical methods. Employing a representative ensemble of water clusters, each made by 22 molecules, diffusion energy barriers between the binding sites are computed using Density Functional Theory. Diffusion rate coefficients are then determined by applying the harmonic approximation of Transition State Theory. The results, in agreement with experimental studies, revealed a wide distribution of diffusion energies. This reflects the intrinsic topological heterogeneity of ASW surfaces, and highlights how surface mobility significantly influences CO's desorption dynamics and, as a consequence, surface-mediated reactivity in interstellar environments. We show that key parameters commonly employed in astrochemical models, like the ratio between binding and diffusion energy, should be carefully revised.