Electrostatic forces from reactive molecular orbitals driving chemical reactions

TL;DR

This paper introduces a physics-based framework that links molecular orbital energy variations to electrostatic forces driving chemical reactions, revealing how reactive orbitals shape reaction pathways and connect with traditional electron transfer diagrams.

Contribution

It uncovers the role of the occupied reactive orbital in generating electrostatic forces that influence nuclear motion, integrating electronic structure with reaction dynamics.

Findings

Reactions classified into four types based on electrostatic force patterns.

Reactive orbital-based electrostatic forces (ROEFs) shape reaction pathways.

Alignment of orbital energy variations with curly arrow diagrams.

Abstract

This study offers a physics-based framework for understanding chemical reactions, unveiling the pivotal role of the occupied reactive orbital (ORO), the most stabilized occupied molecular orbital during a reaction, in driving atomic nuclei along the reaction pathway via electrostatic forces. We show that these electrostatic forces are governed by the negative gradient of orbital energy, establishing a direct link between molecular orbital energy variations and nuclear motion. The forces generated by OROs, termed reactive-orbital-based electrostatic forces (ROEFs), were systematically analyzed across 48 representative reactions. Our findings reveal that reactions can be classified into four distinct types, with two dominant types emerging: those that maintain reaction-direction ROEFs either from the early stages or immediately preceding the transition state. These ROEFs carve distinct grooves along the intrinsic reaction coordinates on the potential energy surface, shaping the reaction pathway. Notably, ORO variations align directly with the curly arrow diagrams widely employed in organic chemistry, bridging the curly arrow-like representation of electron transfer with the rigorous potential energy surface framework. This connection highlights the integration of electronic and nuclear motion theories, offering a unified perspective on the forces that drive chemical transformations. By linking orbital energy variations to nuclear motions, this study establishes a robust framework for understanding the interplay between electronic structure and reaction mechanisms.