title: Empirical correction of nondynamical correlation energy for density functionals.
abstract: To provide an efficient means to address nondynamical correlation, an empirical correction for single and double hybrid density functionals has been formulated. The correction utilizes the highest doubly occupied, lowest unoccupied, and singly occupied generalized Kohn-Sham orbitals and, for potential energy curves, a few additional strongly correlated orbitals. Utilizing proposed nondynamical correlation corrections, hybrid BLYP predicted potential energy curves that fit well to those obtained by ab initio multireference methods for the torsional rotation of ethylene and the automerization of cyclobutadiene. The empirical nondynamical correlation corrections, calculated at the transition structures, also reduce the overall errors of B2K-PLYP for the DBH24 and BH76 barrier height data sets. The proposed empirical correction can efficiently enhance the utility of both single and double hybrid density functionals for chemical situations with moderate to significant nondynamical correlation.
authors.affiliation: Department of Chemistry and Center for Advanced Scientific Computing and Modeling (CASCaM), University of North Texas, Denton, Texas 76203-5017, USA.
authors.forename: Wanyi
authors.initials: W
authors.lastname: Jiang
authors.forename: Chris C
authors.initials: CC
authors.lastname: Jeffrey
authors.forename: Angela K
authors.initials: AK
authors.lastname: Wilson