Linear Free Energy Relationships in Electrostatic Catalysis

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.