Theoretical determination of the binding energies of methanol and related species onto amorphous solid water ice

Abstract

The formation and survival of complex organic molecules (COMs) in cold interstellar environments depends on their interactions with icy dust grain surfaces. Methanol, a key COM detected in cold cores and protoplanetary disks, is believed to form on amorphous solid water (ASW) through surface reactions and reside there until it is desorbed into the gas phase. We present a theoretical study of the binding energies (BEs) of methanol and its photolysis-derived species on ASW clusters by means of dispersion-corrected density functional theory (DFT) using a refined protocol implemented in the Binding Energy Evaluation Platform (BEEP). Molecules capable of hydrogen bonding, such as H2O, CH3OH, HCOOH, and OH, exhibit high BEs and broad BE distributions that reflect the structural heterogeneity of the ASW surface. In contrast, weakly interacting volatiles including CO, CO2, CH4, and CH3 display narrower distributions dominated by dispersion interactions. Open-shell radicals such as CH2OH and OH bind more strongly than HCO and CH3 due to their ability to form directional hydrogen bonds. Incorporation of our BEs into an astrochemical model, in conjunction with a recalculation of the pre-exponential factor using transition state theory, demonstrates the sensitivity of model results to the method of calculation of the grain-surface reaction rates. The new approach generally predicts a higher abundance of radicals on the ice that are key reactants for the formation of COMs when surface diffusion is assumed to be efficient. These findings emphasize the importance of incorporating BEs that have been determined in a self-consistent manner into astrochemical models, and provide reliable theoretical benchmarks for species with limited experimental data.