title: Fock-Matrix Corrections in Density Functional Theory and Use in Embedded Mean-Field Theory.
abstract: We introduce Fock-corrected density functional theory (FCDFT), a semiempirical minimal-basis method part way between density-functional tight binding (DFTB) and DFT. FCDFT contains DFTB-like Fock-matrix contributions calculated using simple pairwise formulas and Slater-Koster transformations, but it also contains the full Kohn-Sham treatment of Coulombic electrostatics. The resulting method is better suited than either minimal-basis DFT or DFTB for modeling the low-level subsystem in embedded mean-field theory (EMFT), improving upon the former by correcting for basis-set incompleteness and upon the latter by properly accounting for electrostatics. EMFT calculations using DFT-in-FCDFT have much smaller errors in orbital energies, dipole moments, and reaction energies than our previous DFT-in-DFT calculations.
authors.affiliation: Centre for Computational Chemistry, School of Chemistry, University of Bristol , Bristol BS8 1TS, United Kingdom.
authors.forename: Kaito
authors.initials: K
authors.lastname: Miyamoto
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Thomas F
authors.initials: TF
authors.lastname: Miller
authors.affiliation: Centre for Computational Chemistry, School of Chemistry, University of Bristol , Bristol BS8 1TS, United Kingdom.
authors.forename: Frederick R
authors.initials: FR
authors.lastname: Manby