Doubly hybrid density functional for accurate descriptions of nonbond interactions, thermochemistry, and thermochemical kinetics.
We develop and validate a density functional, XYG3, based on the adiabatic connection formalism and the Görling-Levy coupling-constant perturbation expansion to the second order (PT2). XYG3 is a doubly hybrid functional, containing 3 mixing parameters. It has a nonlocal orbital-dependent component in the exchange term (exact exchange) plus information about the unoccupied Kohn-Sham orbitals in the correlation part (PT2 double excitation). XYG3 is remarkably accurate for thermochemistry, reaction barrier heights, and nonbond interactions of main group molecules. In addition, the accuracy remains nearly constant with system size.
Zhang
Ying
Y
Department of Chemistry, State Key Laboratory of Physical Chemistry of Solid Surfaces, Center for Theoretical Chemistry, College for Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Xu
Xin
X
Goddard
William A
WA
D055598:Chemical Phenomena; D008956:Models, Chemical; D008958:Models, Molecular; D013816:Thermodynamics