Parameterized local hybrid functionals from density-matrix similarity metrics.
We recently proposed a real-space similarity metric comparing the Kohn-Sham one-particle density matrix to the local spin-density approximation model density matrix [Janesko and Scuseria, J. Chem. Phys. 127, 164117 (2007)]. This metric provides a useful ingredient for constructing local hybrid density functionals that locally mix exact exchange and semilocal density functional theory exchange. Here we present two lines of inquiry: An approximate similarity metric comparing exact versus generalized gradient approximation (GGA), exchange and parameterized mixing functions using these similarity metrics. This approach yields significantly improved thermochemistry, including GGA local hybrids whose thermochemical performance approaches GGA global hybrids.
Janesko
Benjamin G
BG
Department of Chemistry, Rice University, Houston, Texas 77005, USA. bjanesko@rice.edu
Scuseria
Gustavo E
GE
D004583:Electrons; D008958:Models, Molecular; D010825:Physics / Q000379:methods; D013816:Thermodynamics