TY - JOUR
T1 - Exploring Dyson's Orbitals and Their Electron Binding Energies for Conceptualizing Excited States from Response Methodology
AU - Pomogaev, Vladimir
AU - Lee, Seunghoon
AU - Shaik, Sason
AU - Filatov, Michael
AU - Choi, Cheol Ho
N1 - Publisher Copyright:
© 2021 The Authors. Published by American Chemical Society.
PY - 2021/10/14
Y1 - 2021/10/14
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85117792353&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.1c02494
DO - 10.1021/acs.jpclett.1c02494
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
C2 - 34617764
AN - SCOPUS:85117792353
SN - 1948-7185
VL - 12
SP - 9963
EP - 9972
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 40
ER -