TY - JOUR

T1 - Fock-matrix corrections in density functional theory and use in embedded mean-field theory

AU - Miyamoto, Kaito

AU - Miller, Thomas F.

AU - Manby, Frederick R.

PY - 2016/10/17

Y1 - 2016/10/17

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85005978361&partnerID=8YFLogxK

U2 - 10.1021/acs.jctc.6b00685

DO - 10.1021/acs.jctc.6b00685

M3 - Article (Academic Journal)

C2 - 27749063

AN - SCOPUS:85005978361

VL - 12

SP - 5811

EP - 5822

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

SN - 1549-9618

IS - 12

ER -