Exploring Dyson's Orbitals and Their Electron Binding Energies for Conceptualizing Excited States from Response Methodology

Vladimir Pomogaev, Seunghoon Lee, Sason Shaik*, Michael Filatov*, Cheol Ho Choi*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

Abstract

The molecular orbital (MO) concept is a useful tool, which relates the molecular ground-state energy with the energies (and occupations) of the individual orbitals. However, analysis of the excited states from linear response computations is performed in terms of the initial state MOs or some other forms of orbitals, e.g., natural or natural transition orbitals. Because these orbitals lack the respective energies, they do not allow developing a consistent orbital picture of the excited states. Herein, we argue that Dyson's orbitals enable description of the response states compatible with the concepts of molecular orbital theory. The Dyson orbitals and their energies obtained by mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT) for the response ground state are remarkably similar to the canonical MOs obtained by the usual DFT calculation. For excited states, the Dyson orbitals provide a chemically sensible picture of the electronic transitions, thus bridging the chasm between orbital theory and response computations.

Original languageEnglish
Pages (from-to)9963-9972
Number of pages10
JournalJournal of Physical Chemistry Letters
Volume12
Issue number40
DOIs
StatePublished - 14 Oct 2021

Bibliographical note

Publisher Copyright:
© 2021 The Authors. Published by American Chemical Society.

Fingerprint

Dive into the research topics of 'Exploring Dyson's Orbitals and Their Electron Binding Energies for Conceptualizing Excited States from Response Methodology'. Together they form a unique fingerprint.

Cite this