RÉSUMÉ
Many different molecular species have been observed in the interstellar medium. These range from simple diatomic species to saturated organic molecules with several carbon atoms. The latter molecules are assumed to be formed predominantely on the surface of interstellar dust grains. All surface reactions that can proceed under the low interstellar temperatures are exothermic. Their exothermicity can be as high as a few electron volts, which is considerable compared to the thermal energy of the molecules at 10 K. It is postulated that this exothermicity can be used for the desorption of reaction products from the grain. In previous studies, we have shown that translational excitation can lead to desorption, whereas vibrational and rotational excitations are much less efficient in the desorption of surface products. Vibrational excitation is however much more likely upon bond formation than translational excitation. The present study follows energy dissipation upon translational, vibrational, or rotational excitation of admolecules on a surface and its conversion, or lack thereof, to different energy contributions. To this end, thousands of molecular dynamics simulations were performed with an admolecule on top of a surface that received a fixed amount of energy, vibrational, rotational, or translational. Three different surface species have been considered, CO2, H2O, and CH4, spanning a range in binding energies, the number of internal degrees of freedom, and molecular weights. A fast exchange of energy between vibrational stretches is observed, but only very limited exchange to rotational or translation excitation has been found. For the dissipation of energy to the surface, excitation of the surface-admolecule bond is critical. Astrochemical models often assume instantaneous equipartition of energy after a reaction process to estimate the amount of available energy for chemical desorption. Based on the present study, we conclude that this assumption is not justified.
RÉSUMÉ
ConspectusDark molecular clouds have low temperatures of approximately 10 K and experience very little UV irradiation. These clouds are the birthplace of new stars and consist of gas and dust particles. The latter can act as a meeting place to facilitate surface chemistry to form saturated molecules such as formaldehyde, methyl formate, and dimethyl ether. These complex organic molecules or COMs become encapsulated in the ice that forms on the dust grains, and these ices are the precursor for cometary ices and other icy bodies. They likely played a role in bringing material to the early earth.Although these COMs are likely formed on the surfaces of dust grains, several of them have been detected in the gas phase. This means that they have desorbed from the grain under these cold, dark conditions where thermal desorption and photodesorption are negligible. It has been speculated that reactive, or chemical, desorption is responsible for the high gas-phase abundance. After a surface reaction, its products might be vibrationally, translationally, and/or rotationally excited. Dissipation of the excess energy to translational energy can briefly increase the desorption rate, leading to chemical desorption. Astrochemical modellers have added terms to their rate equations to account for this effect. These terms, however, have had little experimental or theoretical verification.In this Account, we use classical molecular dynamics (MD) simulations to give adsorbed molecules a fixed amount of energy as a proxy for excess energy and to record whether this leads to desorption. The excitation energy can be varied freely while keeping all other variables constant. This allows for the study of trends rather than being limited to a single reaction and a single system. The focus is on the dependence of the chemical desorption on the excitation energy, excitation type, and binding energy. Rotational and vibrational excitation was explicitly taken into account. An analytical expression for the chemical desorption probability was obtained in this way. It depends on the binding energy and reaction enthalpy. This expression was then implemented in a gas-grain astrochemical code to simulate the chemical evolution of a dark molecular cloud, and the results were compared against observational abundances of COMs in three different molecular clouds. The results with our new expression based on the MD simulations show good agreement for all species except H2CO, which has both gas-phase and surface-formation routes. This is a significant improvement over models without chemical desorption or with other expressions for chemical desorption, as frequently used by other authors. It is encouraging to see that a general description with a firmer theoretical basis leads to a significant improvement. Understanding chemical desorption can help to explain the unexpectedly high gas-phase abundance of some COMs, and chemical desorption also provides a link between the gas phase and the ice mantle, and its understanding might help in creating a diagnostic tool to learn more about the ice composition.