skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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 ormore » 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.« less

Authors:
 [1];  [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Duke Univ., Durham, NC (United States)
  2. Duke Univ., Durham, NC (United States); South China Normal Univ., Guangzhou (China)
Publication Date:
Research Org.:
Temple Univ., Philadelphia, PA (United States). Energy Frontier Research Center (EFRC) Center for Complex Materials from First Principles (CCM)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1566514
Grant/Contract Number:  
SC0012575
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 123; Journal Issue: 3; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Mei, Yuncai, Li, Chen, Su, Neil Qiang, and Yang, Weitao. Approximating Quasiparticle and Excitation Energies from Ground State Generalized Kohn–Sham Calculations. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.8b10380.
Mei, Yuncai, Li, Chen, Su, Neil Qiang, & Yang, Weitao. Approximating Quasiparticle and Excitation Energies from Ground State Generalized Kohn–Sham Calculations. United States. doi:10.1021/acs.jpca.8b10380.
Mei, Yuncai, Li, Chen, Su, Neil Qiang, and Yang, Weitao. Thu . "Approximating Quasiparticle and Excitation Energies from Ground State Generalized Kohn–Sham Calculations". United States. doi:10.1021/acs.jpca.8b10380.
@article{osti_1566514,
title = {Approximating Quasiparticle and Excitation Energies from Ground State Generalized Kohn–Sham Calculations},
author = {Mei, Yuncai and Li, Chen and Su, Neil Qiang and Yang, Weitao},
abstractNote = {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.},
doi = {10.1021/acs.jpca.8b10380},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 3,
volume = 123,
place = {United States},
year = {2018},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on December 27, 2019
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share: