Year: 2025
Type: article
Abstract: The present work introduces a novel framework to analyze excited-state reactivity by leveraging the redistribution of electron density between two states. This methodology builds upon and extends the Quantum Theory of Atoms in Molecules (QTAIM) and state-specific density partitioning to characterize reactive sites in excited molecules. By employing the electronic redistribution function ∆ρij (r), we demonstrate its ability to delineate reactive sites, describe bond formation dynamics, and predict photoprod- ucts across diverse molecular systems. Examples include the [2+2] cycloaddition of ethylene, the Paternò–Büchi reaction, and thiocarbonyl-initiated cycloadditions, each exhibiting distinct electronic redistribution patterns that govern their excited-state behavior. Furthermore, ∆ρij (r) effectively captures reactivity near conical intersections, offering new insights into degenerate regions of potential energy surfaces. This approach provides a unifying descriptor for excited-state reactivity, bridging classical chemical intuition with a quantum mechanical approach, and sets the stage for developing predictive models for complex photochemical systems.
Author: Cristian J. Guerra
Institution: Universidad Andrés Bello
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
Award: G733791617
OpenAlex ID: W4414535059