Exploring unimolecular reactions in disilanol and ethanol: Insights and challenges

Abstract

Abstract Unimolecular reactions of small silicon oxyhydrides constitute a subset of the full reaction networks that lead to larger species. Previous methods for mechanism discovery have largely been done by manual exploration using chemical intuition. Those works have established general concepts for silanol, SiOH4. The present work is a first attempt to use the automated mechanism discovery of the program AutoMeKin to elucidate the unimolecular reactions of disilanol, Si2OH6. We find that the semi-empirical surfaces used for preliminary exploration insufficiently describe silicon chemistry. As a workaround, we implement an intermediate optimization step to temper these shortcomings. The method recovers the known mechanisms in SiOH4 and C2OH6, which we use for validation. Key results for Si2OH6 include descriptions of relevant elementary reactions, the reaction network, and comparisons with better-known hydrocarbon and silicon hydride reactions. Although the current method shows promise, some shortcomings arise. We discuss the reliability of the generated reaction network and address approaches for further mechanistic understanding of silicon chemistry for material synthesis.