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

Publication ,  Journal Article
Mei, Y; Li, C; Su, NQ; Yang, W
Published in: The journal of physical chemistry. A
January 2019

Quasiparticle energies and fundamental band gaps in particular 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. Results 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. This work highlights the pathway to quasiparticle and excitation energies from ground density functional calculations.

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Published In

The journal of physical chemistry. A

DOI

EISSN

1520-5215

ISSN

1089-5639

Publication Date

January 2019

Volume

123

Issue

3

Start / End Page

666 / 673

Related Subject Headings

  • 5102 Atomic, molecular and optical physics
  • 3407 Theoretical and computational chemistry
  • 3406 Physical chemistry
  • 0307 Theoretical and Computational Chemistry
  • 0306 Physical Chemistry (incl. Structural)
  • 0202 Atomic, Molecular, Nuclear, Particle and Plasma Physics
 

Citation

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Mei, Y., Li, C., Su, N. Q., & Yang, W. (2019). Approximating Quasiparticle and Excitation Energies from Ground State Generalized Kohn-Sham Calculations. The Journal of Physical Chemistry. A, 123(3), 666–673. https://doi.org/10.1021/acs.jpca.8b10380
Mei, Yuncai, Chen Li, Neil Qiang Su, and Weitao Yang. “Approximating Quasiparticle and Excitation Energies from Ground State Generalized Kohn-Sham Calculations.The Journal of Physical Chemistry. A 123, no. 3 (January 2019): 666–73. https://doi.org/10.1021/acs.jpca.8b10380.
Mei Y, Li C, Su NQ, Yang W. Approximating Quasiparticle and Excitation Energies from Ground State Generalized Kohn-Sham Calculations. The journal of physical chemistry A. 2019 Jan;123(3):666–73.
Mei, Yuncai, et al. “Approximating Quasiparticle and Excitation Energies from Ground State Generalized Kohn-Sham Calculations.The Journal of Physical Chemistry. A, vol. 123, no. 3, Jan. 2019, pp. 666–73. Epmc, doi:10.1021/acs.jpca.8b10380.
Mei Y, Li C, Su NQ, Yang W. Approximating Quasiparticle and Excitation Energies from Ground State Generalized Kohn-Sham Calculations. The journal of physical chemistry A. 2019 Jan;123(3):666–673.
Journal cover image

Published In

The journal of physical chemistry. A

DOI

EISSN

1520-5215

ISSN

1089-5639

Publication Date

January 2019

Volume

123

Issue

3

Start / End Page

666 / 673

Related Subject Headings

  • 5102 Atomic, molecular and optical physics
  • 3407 Theoretical and computational chemistry
  • 3406 Physical chemistry
  • 0307 Theoretical and Computational Chemistry
  • 0306 Physical Chemistry (incl. Structural)
  • 0202 Atomic, Molecular, Nuclear, Particle and Plasma Physics