A density matrix functional with occupation number driven treatment of dynamical and nondynamical correlation

D. Rohr, K.D. Pernal, O.V. Gritsenko, E.J. Baerends

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A recently proposed series of corrections to the earliest JK -only functionals has considerably improved the prospects of density matrix functional theory (DMFT). Still, the most advanced of these functionals (correction C3) requires a preselection of the terms in the pair density (r1, r2) involving the bonding and antibonding natural orbitals (NOs) belonging to an electron pair bond. Ideally, a DMFT functional should only depend on the NOs and their occupation numbers, and we propose a functional with an occupation number driven weighing of terms in the pair density. These are formulated as "damping" for certain ranges of occupation numbers of the two-electron cumulant that arises in the expansion of the two-particle density matrix of the paradigmatic two-electron system. This automatic version of C3, which we denote AC3, provides the correct dissociation limit for electron pair bonds and it excellently reproduces the potential energy curves of the multireference configuration interaction (MRCI) method for the dissociation of the electron pair bond in the series of the ten-electron hydrides CH4, NH3, H2 O, and HF. AC3 reproduces closely the experimental equilibrium distances and at Re it yields correlation energies of the ten-electron systems with an average error in the absolute values of only 3.3% compared to the MRCI values. We stress the importance of treatment of strong correlation cases (NO occupation numbers differing significantly from 2.0 and 0.0) by appropriate terms in the cumulant. © 2008 American Institute of Physics.
Original languageEnglish
Pages (from-to)164105
JournalJournal of Chemical Physics
Issue number16
Publication statusPublished - 2008


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