Issue 5, 2024

Visualizing and characterizing excited states from time-dependent density functional theory

Abstract

Time-dependent density functional theory (TD-DFT) is the most widely-used electronic structure method for excited states, due to a favorable combination of low cost and semi-quantitative accuracy in many contexts, even if there are well recognized limitations. This Perspective describes various ways in which excited states from TD-DFT calculations can be visualized and analyzed, both qualitatively and quantitatively. This includes not just orbitals and densities but also well-defined statistical measures of electron–hole separation and of Frenkel-type exciton delocalization. Emphasis is placed on mathematical connections between methods that have often been discussed separately. Particular attention is paid to charge-transfer diagnostics, which provide indicators of when TD-DFT may not be trustworthy due to its categorical failure to describe long-range electron transfer. Measures of exciton size and charge separation that are directly connected to the underlying transition density are recommended over more ad hoc metrics for quantifying charge-transfer character.

Graphical abstract: Visualizing and characterizing excited states from time-dependent density functional theory

Associated articles

Article information

Article type
Perspective
Submitted
01 sep 2023
Accepted
11 dec 2023
First published
12 dec 2023

Phys. Chem. Chem. Phys., 2024,26, 3755-3794

Visualizing and characterizing excited states from time-dependent density functional theory

J. M. Herbert, Phys. Chem. Chem. Phys., 2024, 26, 3755 DOI: 10.1039/D3CP04226J

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