Exploring unimolecular reactions in disilanol and ethanol: Insights and challenges

• Published in: Theoretical chemistry accounts 2023-12, Vol.142 (12), Article 124
• Main Authors: Vázquez, Saulo A., Martínez-Núñez, Emilio, Preston, Thomas J.
• Format: Article
• Language: English
• Subjects: Atomic/Molecular Structure and Spectra; Chemical synthesis; Chemistry; Chemistry and Materials Science; Ethanol; Inorganic Chemistry; Optimization; Organic Chemistry; Physical Chemistry; Silicon; Theoretical and Computational Chemistry
• ISSN: 1432-881X; 1432-2234
• DOI: 10.1007/s00214-023-03062-0

Previous methods for mechanism discovery have largely been done by manual exploration using chemical intuition. The present work is a first attempt to use the automated mechanism discovery of the program AutoMeKin to elucidate the unimolecular reactions of disilanol, Si 2 OH 6 . The semiempirical surfaces computed in the present study insufficiently describe silicon chemistry. As a workaround, we implement an intermediate optimization step to temper these shortcomings. The method recovers the known mechanisms in SiOH 4 and C 2 OH 6 , which we use for validation. Key results for Si 2 OH 6 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.