Double-hybrid density-functional theory made rigorous

Kamal Sharkas, Julien Toulouse, Andreas Savin

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142 Scopus citations

Abstract

We provide a rigorous derivation of a class of double-hybrid approximations, combining Hartree-Fock exchange and second-order Møller-Plesset correlation with a semilocal exchange-correlation density functional. These double-hybrid approximations contain only one empirical parameter and use a density-scaled correlation energy functional. Neglecting density scaling leads to a one-parameter version of the standard double-hybrid approximations. We assess the performance of these double-hybrid schemes on representative test sets of atomization energies and reaction barrier heights, and we compare to other hybrid approximations, including range-separated hybrids. Our best one-parameter double-hybrid approximation, called 1DH-BLYP, roughly reproduces the two parameters of the standard B2-PLYP or B2GP-PLYP double-hybrid approximations, which shows that these methods are not only empirically close to an optimum for general chemical applications but are also theoretically supported.

Original languageEnglish (US)
Article number064113
JournalJournal of Chemical Physics
Volume134
Issue number6
DOIs
StatePublished - Feb 14 2011
Externally publishedYes

Bibliographical note

Funding Information:
K.S. thanks Professor I. Othman (Atomic Energy Commission of Syria) for his support. J.T. and A.S. acknowledge support from Agence Nationale de la Recherche (contract Wademecom 07-BLAN-0272). We also thank J. G. Ángyán for discussions.

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