金星化学的理论动力学研究。SC 1、SCl2和HSC 1的形成和破坏
Theoretical kinetic studies of Venus chemistry. Formation and destruction of SCl, SCl2, and HSCl
摘要：
准确和彻底地表征含有第三行元素硫和氯的化合物的化学性质对于模拟金星大气的组成至关重要。我们已经使用了从头算量子化学和动力学理论的组合来表征一组9个放热反应，涉及外来的硫-氯物种SCl，SCl 2和HSCl，这被认为是存在于金星的大气中的痕量，并包括在不同程度上在已公布的大气模型。在RCCSD（T）水平上，采用耦合团簇理论和三重zeta质量相关一致基组对反应路径进行了表征。对于势垒位于反应物渐近线之上的反应，势垒高度通过四重和五重zeta质量集的单点计算外推到RCCSD（T）完全基组水平。采用捕获理论和过渡态理论预测了反应速率系数。我们已经发现，在某些情况下，加成-消除反应可以与抽象反应竞争，由于硫的倾向，形成高价化合物和中间体，通过重新耦合对键。
英文摘要：
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.
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