Fast and Simple Evaluation of the Catalysis and Selectivity Induced by External Electric Fields

In the oriented external electric field-driven catalysis, the reaction rates and the selectivity of chemical reactions can be tuned at will. The activation barriers of chemical reactions within external electric fields of several strengths and directions can be computationally modelled. However, the calculation of all the required field-dependent transition states and reactants is computationally demanding, especially for large systems. In this paper, we presented a method based on the Taylor expansion of the field-dependent energy of the reactants and transition states in terms of their field-free dipole moments and electrical (hyper)polarizabilities. This approach, called FDBb, allows systematic 1D, 2D, and 3D representations of the activation energy barriers for any strength and direction of the external electric-field. The calculation of the field-dependent FDBb energy barriers has a computational cost several orders of magnitude lower than the explicit electric field optimizations, and the errors of the FDBb barriers are within the range of only 1-2 kcal·mol-1. The achieved accuracy is sufficient for a fast-screening tool to study and predict potential electric field-induced catalysis, regioselectivity, and stereoselectivity.

This work is the result of a long collaboration between the University of Bask country: Miquel Torrent Surcarrat, and our institute: Pau Besalú-Sala, Miquel Solà, and Josep M. Luis and it was recently published in ACS Catalysis:

P. Besalú-Sala, M. Solà, J.M. Luis, and M. Torrent-Sucarrat
“Fast and Simple Evaluation of the Catalysis and Selectivity Induced by External Electric Fields”
ACS Catal. 2021, 11, 14467-14479
DOI: 10.1021/acscatal.1c04247

Girona, Nov. 23, 2021
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