ct0c01029_si_001.xlsx (34.43 kB)
Download file

Representing Exact Electron Densities by a Single Slater Determinant in Finite Basis Sets

Download (34.43 kB)
posted on 08.12.2020, 09:03 authored by Philip Jakobsen, Frank Jensen
The premise for Kohn–Sham density functional theory is that the exact electron density can be generated by a set of orbitals in a single Slater determinant. While this is ensured in a complete basis set, it has been shown that it cannot hold in small basis sets. The present work probes how accurately a reference electron density of the full-CI type can be reproduced by a set of orbitals in a single Slater determinant, as a function of the basis set used for the fitting electron density. The key finding is that the fitting error may be significant for basis sets of double- or triple-ζ quality. It is also shown that it is important that the fitting basis set includes the same basis functions as used for generating the reference electron density. The main limitation in a given basis set is the lack of higher order polarization functions. The error for practical purposes becomes insignificant for basis sets of quadruple-ζ or better quality, and this should be the choice when assessing the accuracy of exchange-correlation functionals by comparing electron densities to accurate reference results generated by wave function methods. The methodology in the present work can be used to transform an electron density from a multideterminant wave function into a set of orbitals in a single Slater determinant, and this may be useful for developing and testing new exchange-correlation functionals.