Astrochemical effect of the fundamental grain surface processes

Abstract

Context. Thermal diffusion is one of the basic processes for the mobility and formation of species on cosmic dust grains. The rate of thermal diffusion is determined by the grain surface temperature, a pre-exponential factor, and an activation energy barrier for diffusion. Due to the lack of laboratory measurements on diffusion, prior astrochemical models usually assume that the diffusion pre-exponential factor is the same as that for desorption. This oversimplification may lead to an uncertainty in the model predictions. Recent laboratory measurements have found that the diffusion pre-exponential factor can differ from that for desorption by several orders of magnitude. However, the newly determined pre-exponential factor has not been tested in astrochemical models so far. Aims. We aim to evaluate the effect of the newly experimentally measured diffusion pre-exponential factor on the chemistry under cold molecular cloud conditions. Methods. We ran a set of parameters with different grain temperatures and diffusion barrier energies using the NAUTILUS astro-chemical code and compared the molecular abundance between the models with the abundance obtained using the experimentally determined pre-exponential factor for diffusion and with the abundance obtained using the values commonly adopted in prior models. Results. We found that statistically, more than half of the total gas-phase and grain surface species are not affected by the new pre-exponential factor after a chemical evolution of 105 yr. The most abundant gas-phase CO and grain surface water ice are not affected by the new pre-exponential factor. For the grain surface species that are affected, compared to the commonly adopted value of the pre-exponential factor for diffusion used in the chemical models, they could be either overproduced or underproduced with the lower diffusion pre-factor used in this work. The former case applies to radicals and the species that serve as reactants, while the latter case applies to complex organic molecules (COMs) on the grain and the species that rarely react with other species. Gas-phase species could also be affected due to the desorption of the grain surface species. The abundance of some gas-phase COMs could be varied by over one order of magnitude depending on the adopted grain surface temperature and/or the ratio of diffusion to desorption energy in the model. Key species whose diffusion pre-exponential factor significantly affects the model predictions were also evaluated, and these species include CH3OH, H2CO, and NO. Conclusions. The results presented in this study show that the pre-exponential factor is one of the basic and important parameters in astrochemical models. It strongly affects the chemistry and should be determined carefully. More experiments to determine the diffusion of grain surface species are helpful for constraining their properties.