Where does the energy go during the interstellar NH$_3$ formation on water ice? A computational study

TL;DR

This study uses quantum simulations to investigate how energy from NH3 formation on water ice in space is dissipated, revealing mechanisms that influence interstellar chemistry and molecule stability.

Contribution

It provides the first detailed atomic-scale analysis of energy dissipation during NH3 formation on water ice, highlighting key mechanisms and their astrophysical implications.

Findings

58-90% of reaction energy absorbed by ice surface

Vibrational mode coupling facilitates energy transfer

Transient ion pair formation accelerates energy dissipation

Abstract

In the coldest (10--20 K) regions of the interstellar medium, the icy surfaces of interstellar grains serve as solid-state supports for chemical reactions. Among their plausible roles, that of third body is advocated, in which the reaction energies of surface reactions dissipate throughout the grain, stabilizing the product. This energy dissipation process is poorly understood at the atomic scale, although it can have a high impact on Astrochemistry. Here, we study, by means of quantum mechanical simulations, the formation of NH3 via successive H-additions to atomic N on water ice surfaces, paying special attention to the third body role. We first characterize the hydrogenation reactions and the possible competitive processes (i.e., H-abstractions), in which the H-additions are more favourable than the H-abstractions. Subsequently, we study the fate of the hydrogenation reaction energies by means of ab initio molecular dynamics simulations. Results show that around 58--90\% of the released energy is quickly absorbed by the ice surface, inducing a temporary increase of the ice temperature. Different energy dissipation mechanisms are distinguished. One mechanism, more general, is based on the coupling of the highly excited vibrational modes of the newly formed species and the libration modes of the icy water molecules. A second mechanism, exclusive during the NH$_3$ formation, is based on the formation of a transient H$_3$O$^+$/NH$_2^-$ ion pair, which significantly accelerates the energy transfer to the surface. Finally, the astrophysical implications of our findings relative to the interstellar synthesis of NH$_3$ and its chemical desorption into the gas are discussed.