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@INPROCEEDINGS{Helbig:280500,
author = {Helbig, Nicole},
title = {{L}ocal reduced-density-matrix-functional theory:
{I}ncorporating static correlation effects in {K}ohn-{S}ham
equations},
school = {Max Planck Institute for the Structure and Dynamics of
Matter},
reportid = {FZJ-2016-00268},
year = {2015},
abstract = {Despite of the great advances in density-functional based
schemes for calculating structural and dynamical properties
in the last decade, we still lack an exchange-correlation
functional which can simultaneously describe equilibrium
properties and the breaking and formation of bonds. At the
same time, schemes based on either many-body perturbation
theory or reduced density matrix functional theory (RDMFT)
suffer from their high computational cost. Here, we present
a novel idea that builds on the knowledge acquired in RDMFT
to construct a density-functional scheme which accurately
incorporates static correlation effects. Within this scheme
the natural orbitals, i.e. the eigenfunctions of the
one-body density matrix, are constrained to be solutions of
a single-particle Schrödinger equation with a local
effective potential. This provides a natural way to connect
an energy eigenvalue spectrum to the natural orbitals. This
energy spectrum is found to reproduce the ionization
potentials of different atoms and molecules very well. In
addition, the dissociation limit of diatomic molecules is
well described without the need to break any spin symmetry,
i.e. this attractive feature of RDMFT is preserved. Due to
the additional constraint the natural orbitals are only
approximately determined which leads to differences between
the unconstrained and the approximate natural orbitals with
the latter being similar to the Kohn-Sham orbitals from a
local density approximation. This suggests that a mixed
density/density-matrix scheme can be developed which takes
the best from both theories: the low computational cost and
accurate description of equilibrium geometries from density
functional theory and the accurate description of static
correlation from reduced density-matrix functional theory.},
organization = {CFEL Seminar, Hamburg (Germany)},
subtyp = {Invited},
cin = {PGI-1 / IAS-1},
cid = {I:(DE-Juel1)PGI-1-20110106 / I:(DE-Juel1)IAS-1-20090406},
pnm = {142 - Controlling Spin-Based Phenomena (POF3-142) / 143 -
Controlling Configuration-Based Phenomena (POF3-143) /
DD000247 - Ab initio description of double and charge
transfer excitations (192610994)},
pid = {G:(DE-HGF)POF3-142 / G:(DE-HGF)POF3-143 /
G:(GEPRIS)192610994},
typ = {PUB:(DE-HGF)31},
url = {https://juser.fz-juelich.de/record/280500},
}