A kinetic perspective of charge transfer reactions: the downfall of hard/soft acid/base interactions

TL;DR

This paper introduces a kinetic perspective into Density Functional Theory to demonstrate that the traditional hard/soft acid/base principle may not hold when reactions are kinetically controlled rather than thermodynamically driven.

Contribution

It extends conceptual DFT to include kinetic factors, revealing limitations of the hard/soft acid/base principle under kinetic control.

Findings

Kinetic control can override thermodynamic predictions in acid/base reactions.

The traditional hard/soft acid/base principle may fail in kinetically controlled scenarios.

A new framework integrating kinetics into DFT is proposed.

Abstract

We show how to incorporate the possibility of kinetic control in the conceptual Density Functional Theory formalism. This allow us to prove that the hard/soft acid/base principle will likely fail when the reactions are not thermodynamically-driven.