Correlation potentials and functionals in Hartree-Fock-Kohn-Sham theory

Chan, Garnet K-L.; Tozer, David J.; Handy, Nicholas C.
August 1997
Journal of Chemical Physics;8/1/1997, Vol. 107 Issue 5, p1536
Academic Journal
We compute molecular Hartree-Fock-Kohn-Sham correlation potentials from ab initio coupled-cluster densities via a modified Zhao, Morrison and Parr [Phys. Rev. A, 50, (1994) 2138] scheme involving exact exchange. We examine the potential for several small systems, and observe complex structure. By fitting a functional expansion to our potentials we obtain a closed-shell functional which is an improvement over other pure correlation functionals in Hartree-Fock-Kohn-Sham calculations. The leading term in our functional is dependent on the number of electrons. Our results lead us to question the utility of correlation defined within the Hartree-Fock-Kohn-Sham scheme, and to consider alternative partitionings of the exchange-correlation energy.


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