Molecular dynamics simulations of D2O ice photodesorption

TL;DR

This study uses molecular dynamics to compare UV photodesorption processes of D2O ice with H2O ice, revealing isotope effects that influence desorption probabilities and mechanisms, with implications for astrochemical models.

Contribution

It provides the first detailed comparison of isotope effects on D2O versus H2O photodesorption using molecular dynamics simulations.

Findings

D2O desorption probability is higher than H2O due to the kick-out mechanism.

D atom photodesorption probability is slightly lower than H atom.

The total D2O photodesorption yield aligns better with experimental data.

Abstract

Molecular dynamics calculations have been performed to study the ultraviolet photodissociation of D2O in an amorphous D2O ice surface at 10-90 K, in order to investigate the influence of isotope effects on the photodesorption processes. As for H2O, the main processes after UV photodissociation are trapping and desorption. There are three desorption processes: D atom, OD radical, and D2O molecule photodesorption. D2O desorption takes places either by direct desorption of a recombined D2O molecule, or when an energetic D atom produced by photodissociation kicks a surrounding D2O molecule out of the surface by transferring part of its momentum. Desorption probabilities are compared quantitatively with those for H2O obtained from previous MD simulations of UV photodissociation of amorphous water ice. The main conclusions are the same, but the average D atom photodesorption probability is smaller than that of the H atom (by about a factor of 0.9) because D has lower kinetic energy than H, whereas the average OD radical photodesorption probability is larger than that of OH (by about a factor of 2.5-2.9 depending on Tice) because OD has higher translational energy than OH for every Tice studied. The average D2O photodesorption probability is larger than that of H2O (by about a factor of 1.4-2.3 depending on Tice), and this is entirely due to a larger contribution of the D2O kick-out mechanism. This is an isotope effect: the kick-out mechanism is more efficient for D2O ice, because the D atom formed after D2O photodissociation has a larger momentum than photogenerated H atoms from H2O, and D transfers momentum more easily to D2O than H to H2O. The total yield has been compared with experiments and the total yield from previous simulations. We find better agreement when we compare experimental yields with calculated yields for D2O ice than when we compare with calculated yields for H2O ice.