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Bartlett, Rodney J.; Ranasinghe, Duminda S., E-mail: bartlett@qtp.ufl.edu2017
AbstractAbstract
[en] Highlights: • A ‘consistent’ KS-DFT obtained by insisting IP condition for all occupied orbitals. • IP condition fixes Kohn-Sham potential for each orbital. • IP condition is a consequence of adiabatic TDDFT. • This also means that the ‘multi-electron self-interaction’, is mitigated. Once electron correlation is included in an effective one-particle operator, one has a correlated orbital theory (COT). One such theory is Kohn-Sham density functional theory (KS-DFT), but there are others. Such methods have the prospect to redefine traditional Molecular Orbital (MO) theory by building a quantitative component upon its conceptual framework. This paper asks the question what conditions should such a theory satisfy and can this be accomplished? One such condition for a COT is that the orbital eigenvalues should satisfy an ionization theorem that generalizes Koopmans’ approximation to the exact principal ionization potentials for every electron in a molecule. Guided by this principle, minimal parameterizations of KS-DFT are made that provide a good approximation to a quantitative MO theory.
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S0009261416309666; Available from http://dx.doi.org/10.1016/j.cplett.2016.12.017; Copyright (c) 2016 Elsevier B.V. All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
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