This project will employ the methods of theoretical and computational chemistry to elucidate the role of hyperconjugation in chemical synthesis.  It will build on the pioneering theoretical work of Mulliken, as well as the early ab initio studies of Ermler and Mulliken on hyperconjugative effects in electrophilic aromatic substitution reactions. The nature of the so- called Whiffen effect, especially in terms of it being observed to result in increased reaction rates by many orders of magnitude, will be studied. In this context, a possible enhancement of the utility of catalysts through predictions of hyperconjugative effects will be examined.  It is planned to utilize ab initio quantum chemistry software platforms as Gaussian, NWChem, and Columbus, with appropriate extensions to incorporate techniques of artificial intelligence (AI), particularly symbolic computation in applications to structure and reaction rates. It is planned to use potential energy surface and molecular properties calculations to confirm the role of hyperconjugation in the contest of chemical reactions. The use of a gpu-based implementation of the Ermler group’s parallel spin-orbit configuration interaction code, currently resident at the Texas Advanced Computing Center and the National Energy Research Scientific Computing Center, for calculations of hyperconjugative effects involving heavy-metal-containing catalysts will be investigated.

Theoretical and computational study of the role of hyperconjugation in chemical synthesis

ACS Fall 2021

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