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

Pomogaev, Vladimir and Lee, Seunghoon and Shaik, Sason and Filatov, Michael and Choi, Cheol Ho (2021) Exploring Dyson’s Orbitals and Their Electron Binding Energies for Conceptualizing Excited States from Response Methodology. Journal of Physical Chemistry Letters, 12 (40). pp. 9963-9972. ISSN 1948-7185. doi:10.1021/acs.jpclett.1c02494.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription
Pomogaev, Vladimir0000-0003-4774-3998
Lee, Seunghoon0000-0003-3665-587X
Shaik, Sason0000-0001-7643-9421
Filatov, Michael0000-0002-1541-739X
Choi, Cheol Ho0000-0002-8757-1396
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.
Funding AgencyGrant Number
Samsung Science and Technology FoundationSSTF-BA1701-12
National Research Foundation of Korea2019H1D3A2A02102948
National Research Foundation of Korea2020R1A2C2008246
National Research Foundation of Korea2020R1A5A1019141
Subject Keywords:Electrical energy, Energy, Electron correlation, Excited states, Molecules
Issue or Number:40
Record Number:CaltechAUTHORS:20211008-224623460
Persistent URL:
Official Citation:Exploring Dyson’s Orbitals and Their Electron Binding Energies for Conceptualizing Excited States from Response Methodology. Vladimir Pomogaev, Seunghoon Lee, Sason Shaik, Michael Filatov, and Cheol Ho Choi. The Journal of Physical Chemistry Letters 2021 12 (40), 9963-9972; DOI: 10.1021/acs.jpclett.1c02494
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:111325
Deposited By: George Porter
Deposited On:12 Oct 2021 14:23
Last Modified:02 Nov 2021 22:47

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