Double-hybrid density-functional theory made rigorous
Abstract
We provide a rigorous derivation of a class of double-hybrid approximations, combining Hartree-Fock exchange and second-order Moller-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.
Keywords
Cite
@article{arxiv.1012.5823,
title = {Double-hybrid density-functional theory made rigorous},
author = {Kamal Sharkas and Julien Toulouse and Andreas Savin},
journal= {arXiv preprint arXiv:1012.5823},
year = {2011}
}