Towards nonlocal density functionals by explicit modeling of the exchangecorrelation hole in inhomogeneous systems
(2013) In Physical Review A (Atomic, Molecular and Optical Physics) 87(2). Abstract
 We put forward an approach for the development of a nonlocal density functional by a direct modeling of the shape of exchangecorrelation (xc) hole in inhomogeneous systems. The functional is aimed at giving an accurate xc energy and an accurate corresponding xc potential even in difficult neardegeneracy situations such as molecular bond breaking. In particular we demand that: (1) the xc hole properly contains 1 electron, (2) the xc potential has the asymptotic 1/r behavior outside finite systems, and (3) the xc potential has the correct step structure related to the derivative discontinuities of the xc energy functional. None of the currently existing functionals satisfies all these requirements. These demands are achieved by screening... (More)
 We put forward an approach for the development of a nonlocal density functional by a direct modeling of the shape of exchangecorrelation (xc) hole in inhomogeneous systems. The functional is aimed at giving an accurate xc energy and an accurate corresponding xc potential even in difficult neardegeneracy situations such as molecular bond breaking. In particular we demand that: (1) the xc hole properly contains 1 electron, (2) the xc potential has the asymptotic 1/r behavior outside finite systems, and (3) the xc potential has the correct step structure related to the derivative discontinuities of the xc energy functional. None of the currently existing functionals satisfies all these requirements. These demands are achieved by screening the exchange hole in such a way that the paircorrelation function is symmetric and satisfies the sum rule. These two features immediately imply (1) and (2) while the explicit dependence of the exchange hole on the KohnSham orbitals implies (3). Preliminary calculations show an improved physical description of the dissociating hydrogen molecule. Though the total energy is still far from perfect, the binding curve from our nonlocal density functional provides a significant improvement over the local density approximation. DOI: 10.1103/PhysRevA.87.022514 (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/3670229
 author
 Giesbertz, K. J. H. ; van Leeuwen, R. and von Barth, Ulf ^{LU}
 organization
 publishing date
 2013
 type
 Contribution to journal
 publication status
 published
 subject
 in
 Physical Review A (Atomic, Molecular and Optical Physics)
 volume
 87
 issue
 2
 article number
 022514
 publisher
 American Physical Society
 external identifiers

 wos:000315479700010
 scopus:84874526997
 ISSN
 10502947
 DOI
 10.1103/PhysRevA.87.022514
 language
 English
 LU publication?
 yes
 id
 f7f8ecced3d94daea968bf88ece67e3d (old id 3670229)
 date added to LUP
 20160401 09:52:27
 date last changed
 20210922 03:26:28
@article{f7f8ecced3d94daea968bf88ece67e3d, abstract = {We put forward an approach for the development of a nonlocal density functional by a direct modeling of the shape of exchangecorrelation (xc) hole in inhomogeneous systems. The functional is aimed at giving an accurate xc energy and an accurate corresponding xc potential even in difficult neardegeneracy situations such as molecular bond breaking. In particular we demand that: (1) the xc hole properly contains 1 electron, (2) the xc potential has the asymptotic 1/r behavior outside finite systems, and (3) the xc potential has the correct step structure related to the derivative discontinuities of the xc energy functional. None of the currently existing functionals satisfies all these requirements. These demands are achieved by screening the exchange hole in such a way that the paircorrelation function is symmetric and satisfies the sum rule. These two features immediately imply (1) and (2) while the explicit dependence of the exchange hole on the KohnSham orbitals implies (3). Preliminary calculations show an improved physical description of the dissociating hydrogen molecule. Though the total energy is still far from perfect, the binding curve from our nonlocal density functional provides a significant improvement over the local density approximation. DOI: 10.1103/PhysRevA.87.022514}, author = {Giesbertz, K. J. H. and van Leeuwen, R. and von Barth, Ulf}, issn = {10502947}, language = {eng}, number = {2}, publisher = {American Physical Society}, series = {Physical Review A (Atomic, Molecular and Optical Physics)}, title = {Towards nonlocal density functionals by explicit modeling of the exchangecorrelation hole in inhomogeneous systems}, url = {http://dx.doi.org/10.1103/PhysRevA.87.022514}, doi = {10.1103/PhysRevA.87.022514}, volume = {87}, year = {2013}, }