Self-interaction-free exchange-correlation functional for thermochemistry and kinetics.
We develop a self-interaction-free exchange-correlation functional which is very accurate for thermochemistry and kinetics. This is achieved by theoretical construction of the functional form and nonlinear fitting. We define a simple interpolation of the adiabatic connection that uses exact exchange, generalized gradient approximation (GGA) and meta-GGA functionals. The performance is optimized by fitting a small number of empirical parameters. Overall the new functional improves significantly upon hybrids and meta-GGAs while correctly describing one-electron systems. The mean absolute error on a large set of reaction barriers is reduced to 1.99 kcal/mol.
Mori-Sánchez
Paula
P
Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.
Cohen
Aron J
AJ
Yang
Weitao
W
D007700:Kinetics; D008956:Models, Chemical; D008962:Models, Theoretical; D013696:Temperature; D013816:Thermodynamics