http://arxiv.org/abs/2012.02054
Accurate and thorough characterization of the chemistry of compounds containing the third-row elements sulfur and chlorine is critical for modeling the composition of the atmosphere of Venus. We have used a combination of ab initio quantum chemistry and kinetic theory to characterize a group of nine exothermic reactions that involve the exotic sulfur-chlorine species SCl, SCl2, and HSCl, which are thought to be present in trace quantities in the atmosphere of Venus and are included to various degrees in the published atmospheric models. Reaction pathways were characterized with coupled cluster theory at the RCCSD(T) level with triple zeta quality correlation consistent basis sets. For reactions with barriers that lie above the reactant asymptote, the barrier height was extrapolated to the RCCSD(T) complete basis set level via single-point calculations with quadruple and quintuple zeta quality sets. Rate coefficients were predicted with capture theory and transition state theory as appropriate. We have found that in some cases addition-elimination reactions can compete with abstraction reactions due to the tendency of sulfur to form hypervalent compounds and intermediates via recoupled pair bonding.
D. Woon, D. Maffucci and E. Herbst
Fri, 4 Dec 20
23/77
Comments: Includes 3 tables and 5 figures, plus Supplemental Information (cartesian structures, energies, and ZPE corrections)