Miyamoto Kaito, Miller Thomas F, Manby Frederick R
Centre for Computational Chemistry, School of Chemistry, University of Bristol , Bristol BS8 1TS, United Kingdom.
Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
J Chem Theory Comput. 2016 Dec 13;12(12):5811-5822. doi: 10.1021/acs.jctc.6b00685. Epub 2016 Nov 4.
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.
我们引入了福克校正密度泛函理论（FCDFT），这是一种介于密度泛函紧束缚（DFTB）和密度泛函理论（DFT）之间的半经验最小基方法。FCDFT包含使用简单成对公式和斯莱特-科斯特变换计算的类似DFTB的福克矩阵贡献，但它也包含对库仑静电的完整科恩-沙姆处理。由此产生的方法比最小基DFT或DFTB更适合于在嵌入式平均场理论（EMFT）中对低层次子系统进行建模，通过校正基组不完整性改进了前者，通过正确考虑静电改进了后者。与我们之前的DFT-in-DFT计算相比，使用DFT-in-FCDFT的EMFT计算在轨道能量、偶极矩和反应能量方面的误差要小得多。
