Improved Electronic Excitation Energies from Shape-Corrected Semilocal Kohn-Sham Potentials

Alex P. Gaiduk, Dzmitry S. Firaha, and Viktor N. Staroverov
Phys. Rev. Lett. 108, 253005 – Published 20 June 2012
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Abstract

We propose a general method for obtaining accurate valence and Rydberg excitation energies from standard density-functional approximations in adiabatic linear-response time-dependent density-functional theory. The method consists in modeling the sum of Hartree (Coulomb) and exchange-correlation potentials, vHXC(r), by the Hartree-exchange-correlation potential of the corresponding partially ionized system in which a fraction of electron charge (δ=0.15 to 0.30, depending on the functional) is removed from the highest occupied Kohn-Sham orbital level. The model potential is less repulsive and closer to exact in valence and near asymptotic regions, so it yields more accurate Kohn-Sham orbitals and orbital eigenvalues. By applying this scheme to conventional local, semilocal, and hybrid density-functional approximations, we improve their accuracy for Rydberg excitations by almost an order of magnitude without sacrificing the already good performance for valence transitions.

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  • Received 2 April 2012

DOI:https://doi.org/10.1103/PhysRevLett.108.253005

© 2012 American Physical Society

Authors & Affiliations

Alex P. Gaiduk, Dzmitry S. Firaha, and Viktor N. Staroverov

  • Department of Chemistry, The University of Western Ontario, London, Ontario N6A 5B7, Canada

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Issue

Vol. 108, Iss. 25 — 22 June 2012

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