부산대학교 도서관

The hydrogen abstraction reaction between H and H$_2$S, yielding HS and H$_2$ as products, has been studied within the framework of interstellar surface chemistry. High-temperature rate constants up to 2000 K are calculated in the gas phase and are in agreement with previously reported values. Subsequently low-temperature rate constants down to 55 K are presented for the first time that are of interest to astrochemistry, i.e., covering both bimolecular and unimolecular reaction mechanisms. For this, a so-called implicit surface model is used. Strictly speaking, this is a structural gas-phase model in which the restriction of the rotation in the solid state is taken into account. The calculated kinetic isotope effects are explained in terms of difference in activation and delocalization. All rate constants are calculated at the UCCSD(T)-F12/cc-VTZ-F12 level of theory. Finally, we show that the energetics of the reaction is only affected to a small extent by the presence of H$_2$O or H$_2$S molecular clusters that simulate an ice surface, calculated at the MPWB1K/def2-TZVP level of theory.
Comment: Accepted for publication in Journal of Physical Chemistry A http://pubs.acs.org/doi/pdfplus/10.1021/acs.jpca.7b10296