A correlated orbital theory (COT) has an effective one-particle operator which include electron correlation. Kohn-Sham density functional theory (KS-DFT), can be considered as a COT. One of the conditions that COT should satisfy is that orbital eigenvalues approximate the exact principal ionization potentials for occupied orbital in a molecule. Under GKS-DFT formalism, the IP condition is a consequence of adiabatic TDDFT and beyond being an accurate approach for excitation energies. When an electron is excited into the continuum, all the KS ground state orbital energies should be good approximations to IP’s. To satisfy the COT IP condition for mth orbital, -IPm=εm=〈φm|H+J-K+Σcc|φm〉≈〈φm|H+J+Vxc|φm〉demands that Vxc be an accurate approximation to the non-local,-K+Σcc, where H, J, K, Σcc, and Vxc stands for one-electron Hamiltonian, coulomb integral, exchange integral, self-energy, and coulomb and exchange potential respectively. Guided by this principle minimally parameterized QTP functionals were constructed. These QTP functional showed less self-interaction error, correct bond dissociating curves, correct long-range behavior for charge transfer complex, and competitive thermochemical accuracy when compare to similar functionals. QTP00 functional showed excellent results for core excitations and QTP01functional also showed the accurate prediction of valence and Rydberg excitation. QTP02 functional is based on ωB97 formalism and an improvement upon QTP00 and QTP01.

Power of exact using conditions to develop density functionals

254th National Meeting (2017)

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