Relationships between Orbital Energies, Optical and Fundamental Gaps, and Exciton Shifts in Approximate Density Functional Theory and Quasiparticle Theory

• Published in: Journal of chemical theory and computation 2020-07, Vol.16 (7), p.4337-4350
• Main Authors: Shu, Yinan, Truhlar, Donald G
• Format: Article
• Language: English
• Subjects: Density functional theory; Excitation; Excitons; Green's functions; Quantum Electronic Structure; Time dependence
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.0c00320

The relationships between Kohn–Sham (KS) and generalized KS (GKS) density functional orbital energies and fundamental gaps or optical gaps raise many interesting questions including the physical meanings of KS and GKS orbital energies when computed with currently available approximate density functionals (ADFs). In this work, by examining three diverse databases with various ADFs, we examine such relations from the point of view of the exciton shift of quasiparticle theory. We start by calculating a large number of excitation energies by time-dependent density functional theory (TDDFT) with a large number of ADFs. To relate the exciton shift implicit in TDDFT to the exciton shift that is explicit in Green’s function theory, we define the exciton shift in TDDFT as the difference of the response shift and the quasiparticle shift. We found a strong correlation between the response shift and the amount of Hartree–Fock exchange included in the density functional, with the response shift varying between −1 and 5 eV. This range is an order of magnitude larger than the mean errors of the TDDFT excitation energies. This result suggests that, with currently available functionals, the KS or GKS orbital energies should be treated as intermediate mathematical variables in the calculation of excitation energies rather than as the energies of independent-particle reference states for quasiparticle theory.