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
16 صفر 1445
Accepted
27 جمادى الأولى 1445
First published
28 جمادى الأولى 1445

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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