Linear Free Energy Relationships in Electrostatic Catalysis

Norah M. Hoffmann, Xiao Wang, Timothy C. Berkelbach

Research output: Contribution to journalArticlepeer-review

Abstract

The use of electric fields to modify chemical reactions is a promising, emerging technique in catalysis. However, there exist few guiding principles, and rational design requires assumptions about the transition state or explicit atomistic calculations. Here, we present a linear free energy relationship, familiar in other areas of physical organic chemistry and catalysis, that microscopically relates field-induced changes in the activation energy to those in the reaction energy, connecting kinetic and thermodynamic behaviors. We verify our theory using first-principles electronic structure calculations of a symmetric SN2 reaction and the dehalogenation of an aryl halide on gold surfaces and observe hallmarks of linear free energy relationships, such as the shifting to early and late transition states. We also report and explain a counterintuitive case, where the constant of proportionality relating the activation and reaction energies is negative, such that stabilizing the product increases the activation energy, that is, opposite of the Bell-Evans-Polanyi principle.

Original languageEnglish (US)
Pages (from-to)8237-8241
Number of pages5
JournalACS Catalysis
Volume12
Issue number14
DOIs
StatePublished - Jul 15 2022

Keywords

  • Bell-Evans-Polanyi principle
  • density functional theory
  • electric fields
  • linear free energy relationship

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry

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