Electronic Excitations Through the Prism of Mean-Field Decomposition Techniques

TL;DR

This paper investigates how mean-field decomposition techniques can interpret electronic excitations in molecules, providing insights into excited-state properties and functional approximation differences without relying on molecular orbitals.

Contribution

It introduces a novel application of mean-field decomposition to analyze electronic excitations, offering new tools for understanding and validating excited-state calculations.

Findings

Decomposed results reveal the nature of electronic excitations.

Analysis of properties changes upon state transitions.

Insights into functional approximation differences in DFT.

Abstract

The potential of mean-field decomposition techniques in interpreting electronic transitions in molecules is explored, particularly, the usefulness of these for offering computational signatures of different classes of such excitations. When viewed as a conceptual lens for this purpose, decomposed results are presented for ground- and excited-state energies and dipole moments of selected prototypical organic dyes, and the discrete nature of these properties as well as how they change upon transitioning from one state to another is analyzed without recourse to a discussion based on the involved molecular orbitals. On the basis of results obtained both with and without an account of continuum solvation, our work is further intended to shed new light on practical and pathological differences in between various functional approximations in orbital-optimized Kohn-Sham density functional theory for excited states, equipping practitioners and developers in the field with new probes and possible validation tools.