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Charge transfer excitation energies from ground state density functional theory calculations.

Publication ,  Journal Article
Mei, Y; Yang, W
Published in: The Journal of chemical physics
April 2019

Calculating charge transfer (CT) excitation energies with high accuracy and low computational cost is a challenging task. Kohn-Sham density functional theory (KS-DFT), due to its efficiency and accuracy, has achieved great success in describing ground state problems. To extend to excited state problems, our group recently demonstrated an approach with good numerical results to calculate low-lying and Rydberg excitation energies of an N-electron system from a ground state KS or generalized KS calculations of an (N - 1)-electron system via its orbital energies. In the present work, we explore further the same methodology to describe CT excitations. Numerical results from this work show that performance of conventional density functional approximations (DFAs) is not as good for CT excitations as for other excitations due to the delocalization error. Applying localized orbital scaling correction (LOSC) to conventional DFAs, a recently developed method in our group to effectively reduce the delocalization error, can improve the results. Overall, the performance of this methodology is better than time dependent DFT (TDDFT) with conventional DFAs. In addition, it shows that results from LOSC-DFAs in this method reach similar accuracy to other methods, such as ΔSCF, G0W0 with Bethe-Salpeter equations, particle-particle random phase approximation, and even high-level wavefunction methods like CC2. Our analysis shows that the correct 1/R trend for CT excitation can be captured from LOSC-DFA calculations, stressing that the application of DFAs with the minimal delocalization error is essential within this methodology. This work provides an efficient way to calculate CT excitation energies from ground state DFT.

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Published In

The Journal of chemical physics

DOI

EISSN

1089-7690

ISSN

0021-9606

Publication Date

April 2019

Volume

150

Issue

14

Start / End Page

144109

Related Subject Headings

  • Chemical Physics
  • 51 Physical sciences
  • 40 Engineering
  • 34 Chemical sciences
  • 09 Engineering
  • 03 Chemical Sciences
  • 02 Physical Sciences
 

Citation

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Mei, Y., & Yang, W. (2019). Charge transfer excitation energies from ground state density functional theory calculations. The Journal of Chemical Physics, 150(14), 144109. https://doi.org/10.1063/1.5087883
Mei, Yuncai, and Weitao Yang. “Charge transfer excitation energies from ground state density functional theory calculations.The Journal of Chemical Physics 150, no. 14 (April 2019): 144109. https://doi.org/10.1063/1.5087883.
Mei Y, Yang W. Charge transfer excitation energies from ground state density functional theory calculations. The Journal of chemical physics. 2019 Apr;150(14):144109.
Mei, Yuncai, and Weitao Yang. “Charge transfer excitation energies from ground state density functional theory calculations.The Journal of Chemical Physics, vol. 150, no. 14, Apr. 2019, p. 144109. Epmc, doi:10.1063/1.5087883.
Mei Y, Yang W. Charge transfer excitation energies from ground state density functional theory calculations. The Journal of chemical physics. 2019 Apr;150(14):144109.

Published In

The Journal of chemical physics

DOI

EISSN

1089-7690

ISSN

0021-9606

Publication Date

April 2019

Volume

150

Issue

14

Start / End Page

144109

Related Subject Headings

  • Chemical Physics
  • 51 Physical sciences
  • 40 Engineering
  • 34 Chemical sciences
  • 09 Engineering
  • 03 Chemical Sciences
  • 02 Physical Sciences