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We introduce an orbital-optimized double-hybrid (DH) scheme using the optimized-effective-potential (OEP) method. The orbitals are optimized using a local potential corresponding to the complete exchange-correlation energy expression including the second-order M{{\o}}ller-Plesset (MP2) correlation contribution. We have implemented a one-parameter version of this OEP-based self-consistent DH scheme using the BLYP density-functional approximation and compared it to the corresponding non-self-consistent DH scheme for calculations on a few closed-shell atoms and molecules. While the OEP-based self-consistency does not provide any improvement for the calculations of ground-state total energies and ionization potentials, it does improve the accuracy of electron affinities and restores the meaning of the LUMO orbital energy as being connected to a neutral excitation energy. Moreover, the OEP-based self-consistent DH scheme provides reasonably accurate exchange-correlation potentials and correlated densities., Comment: in The Journal of Chemical Physics, American Institute of Physics, 2016

Range-separated density-functional theory is an alternative approach to Kohn-Sham density-functional theory. The strategy of range-separated density-functional theory consists in separating the Coulomb electron-electron interaction into long-range and short-range components, and treating the long-range part by an explicit many-body wave-function method and the short-range part by a density-functional approximation. Among the advantages of using many-body methods for the long-range part of the electron-electron interaction is that they are much less sensitive to the one-electron atomic basis compared to the case of the standard Coulomb interaction. Here, we provide a detailed study of the basis convergence of range-separated density-functional theory. We study the convergence of the partial-wave expansion of the long-range wave function near the electron-electron coalescence. We show that the rate of convergence is exponential with respect to the maximal angular momentum L for the long-range wave function, whereas it is polynomial for the case of the Coulomb interaction. We also study the convergence of the long-range second-order M{{\o}}ller-Plesset correlation energy of four systems (He, Ne, N2, and H2O) with the cardinal number X of the Dunning basis sets cc-p(C)VXZ, and find that the error in the correlation energy is best fitted by an exponential in X. This leads us to propose a three-point complete-basis-set extrapolation scheme for range-separated density-functional theory based on an exponential formula.

A generalized adiabatic connection for ensembles (GACE) is presented. In contrast to the traditional adiabatic connection formulation, both ensemble weights and interaction strength can vary along a GACE path while the ensemble density is held fixed. The theory is presented for non-degenerate two-state ensembles but it can in principle be extended to any ensemble of fractionally occupied excited states. Within such a formalism an exact expression for the ensemble exchange-correlation density-functional energy, in terms of the conventional ground-state exchange-correlation energy, is obtained by integration over the ensemble weight. Stringent constraints on the functional are thus obtained when expanding the ensemble exchange-correlation energy through second order in the ensemble weight. For illustration purposes, the analytical derivation of the GACE is presented for the H2 model system in a minimal basis, leading thus to a simple density-functional approximation to the ensemble exchange-correlation energy. Encouraging results were obtained with this approximation for the description in a large basis of the first ^1\Sigma^+_g excitation in H2 upon bond stretching. Finally, a range-dependent GACE has been derived, providing thus a pathway to the development of a rigorous state-average multi-determinant density-functional theory., Comment: 3 figures

We present a graphical analysis of the adiabatic connections underlying double-hybrid density-functional methods that employ second-order perturbation theory. Approximate adiabatic connection formulae relevant to the construction of these functionals are derived and compared directly with those calculated using accurate ab initio methods. The discontinuous nature of the approximate adiabatic integrands is emphasized, the discontinuities occurring at interaction strengths which mark the transitions between regions that are: (i) described predominantly by second- order perturbation theory (ii) described by a mixture of density-functional and second-order perturbation theory contributions and (iii) described purely by density-functional theory. Numerical examples are presented for a selection of small molecular systems and van der Waals dimers. The impacts of commonly used approximations in each of the three sections of the adiabatic connection are discussed along with possible routes for the development of improved double-hybrid methodologies., Comment: 42 pages, 3 figures