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arXiv · 1109.1485

Rigorous formulation of two-parameter double-hybrid density-functionals

Emmanuel Fromager
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Abstract

A two-parameter extension of the density-scaled double hybrid approach of Sharkas et al. [J. Chem. Phys. 134, 064113 (2011)] is presented. It is based on the explicit treatment of a fraction of multideterminantal exact exchange. The connection with conventional double hybrids is made when neglecting density scaling in the correlation functional as well as second-order corrections to the density. In this context, the fraction ac of second-order Møller-Plesset (MP2) correlation energy is not necessarily equal to the square of the fraction ax of Hartree-Fock exchange. More specifically, it is shown that ac \leq ax2, a condition that conventional semi-empirical double hybrids actually fulfill. In addition, a new procedure for calculating the orbitals, which has a better justification than the one routinely used, is proposed. Referred to as λ1 variant, the corresponding double hybrid approximation has been tested on a small set consisting of H2, N2, Be2, Mg2, and Ar2. Three conventional double hybrids (B2-PLYP, B2GP-PLYP, and PBE0-DH) have been considered. Potential curves obtained with λ1- and regular double hybrids can, in some cases, differ significantly. In particular, for the weakly bound dimers, the λ1 variants bind systematically more than the regular ones, which is an improvement in many but not all cases. Including density scaling in the correlation functionals may of course change the results significantly. Moreover, optimized effective potentials based on a partially-interacting system could also be used to generate proper orbitals. Work is currently in progress in those directions.

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Emmanuel Fromager. 2012-01-11. Rigorous formulation of two-parameter double-hybrid density-functionals. https://doi.org/10.1063/1.3671384

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