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Exploring unimolecular reactions in disilanol and ethanol: Insights and challenges

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Abstract

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, Si2OH6. 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 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.

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Acknowledgements

SAV and EM-N acknowledge the financial support from Ministerio de Ciencia e Innovación (grant number PID2019-107307RB-100) and Xunta de Galicia (grant number ED431C 2021/40).

Funding

Partial financial support was received from Ministerio de Ciencia e Innovación (grant number PID2019-107307RB-100) and Xunta de Galicia (grant number ED431C 2021/40).

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Authors and Affiliations

  1. Departamento de Química Física, Facultade de Química, Universidade de Santiago de Compostela, 15782, Santiago de Compostela, Spain

    Saulo A. Vázquez & Emilio Martínez-Núñez

  2. Soldrevet Chemistry, Herefossveien 2117, 4766, Herefoss, Norway

    Thomas J. Preston

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  1. Saulo A. Vázquez
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  2. Emilio Martínez-Núñez
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  3. Thomas J. Preston
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TJP performed the calculations. SAV, EM-N and TJP wrote the manuscript. All authors reviewed the manuscript.

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Correspondence to Emilio Martínez-Núñez or Thomas J. Preston.

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Vázquez, S.A., Martínez-Núñez, E. & Preston, T.J. Exploring unimolecular reactions in disilanol and ethanol: Insights and challenges. Theor Chem Acc 142, 124 (2023). https://doi.org/10.1007/s00214-023-03062-0

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