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Approximating Quasiparticle and Excitation Energies from Ground State Generalized Kohn–Sham Calculations

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [1];  [1];  [2]
  1. Duke Univ., Durham, NC (United States)
  2. Duke Univ., Durham, NC (United States); South China Normal Univ., Guangzhou (China)
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Quasiparticle energies and fundamental band gaps specifically are critical properties of molecules and materials. It was rigorously established that the generalized Kohn–Sham HOMO and LUMO orbital energies are the chemical potentials of electron removal and addition and thus good approximations to band edges and fundamental gaps from a density functional approximation (DFA) with minimal delocalization error. For other quasiparticle energies, their connection to the generalized Kohn–Sham orbital energies has not been established but remains highly interesting. We provide the comparison of experimental quasiparticle energies for many finite systems with calculations from the GW Green function and localized orbitals scaling correction (LOSC), a recently developed correction to semilocal DFAs, which has minimal delocalization error. Extensive results with over 40 systems clearly show that LOSC orbital energies achieve slightly better accuracy than the GW calculations with little dependence on the semilocal DFA, supporting the use of LOSC DFA orbital energies to predict quasiparticle energies. This also leads to the calculations of excitation energies of the N-electron systems from the ground state DFA calculations of the (N – 1)-electron systems. Findings show good performance with accuracy similar to TDDFT and the delta SCF approach for valence excitations with commonly used DFAs with or without LOSC. For Rydberg states, good accuracy was obtained only with the use of LOSC DFA. Our report highlights the pathway to quasiparticle and excitation energies from ground density functional calculations.
Research Organization:
Temple Univ., Philadelphia, PA (United States). Energy Frontier Research Center (EFRC) Center for Complex Materials from First Principles (CCM)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012575
OSTI ID:
1566514
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 3 Vol. 123; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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