Work

Double-hybrid density-functional theory made rigorous

Year: 2011

Type: article

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.

Source: The Journal of Chemical Physics

DOI: 10.1063/1.3544215

Authors: Kamal Sharkas, Julien Toulouse, Andreas Savin

Institutions: Centre National de la Recherche Scientifique, Laboratoire de Chimie Théorique, Atomic Energy Commission of Syria, Université Pierre-et-Marie-Curie

Language: English

Topic: Advanced Chemical Physics Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: green

Funders: Agence Nationale de la Recherche, Atomic Energy Commission of Syria

Award: WAve Function and DEnsity Functional MEthods COMbined: efficient treatment of challenging cases of electron correlation in molecules and materials