Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published October 14, 2021 | Published + Supplemental Material
Journal Article Open

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

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.

Additional Information

© 2021 The Authors. Published by American Chemical Society. Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) Received: July 30, 2021; Accepted: September 22, 2021; Published: October 7, 2021. This work was supported by the Samsung Science and Technology Foundations Grant SSTF-BA1701-12 (to C.H.C.) for fundamental theory developments and the NRF Grants 2019H1D3A2A02102948 (to M.F.) and 2020R1A2C2008246 and 2020R1A5A1019141 (to C.H.C.) funded by the Ministry of Science and ICT for applications of the developed methodologies. The authors declare no competing financial interest.

Attached Files

Published - acs.jpclett.1c02494.pdf

Supplemental Material - jz1c02494_si_001.pdf

Files

acs.jpclett.1c02494.pdf
Files (7.8 MB)
Name Size Download all
md5:618fad56c42f0daf012d5d3ad7b5a37f
1.3 MB Preview Download
md5:a5810e270d97c77658f4cff7534b1893
6.5 MB Preview Download

Additional details

Created:
August 20, 2023
Modified:
October 23, 2023