Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	Performance of the constrained minimization of the total energy in density functional approximations: the electron repulsion density and potential
Δημιουργός/Συγγραφέας:	Pitts T. Gidopoulos N.I. [EL] Λαθιωτάκης, Νεκτάριος N.[EN] Lathiotakis, Nektarios N.
Εκδότης:	Springer Heidelberg
Ημερομηνία:	2018
Γλώσσα:	Αγγλικά
ISSN:	1434-6028
DOI:	10.1140/epjb/e2018-90123-8
Περίληψη:	In the constrained minimization method of Gidopoulos and Lathiotakis [N.I. Gidopoulos, N.N. Lathiotakis, J. Chem. Phys. 136, 224109 (2012)], the Hartree exchange and correlation Kohn-Sham potential of a finite N-electron system is replaced by the electrostatic potential of an effective charge density that is everywhere positive and integrates to a charge of N − 1 electrons. The optimal effective charge density (electron repulsion density, ρrep) and the corresponding optimal effective potential (electron repulsion potential vrep) are obtained by minimizing the electronic total energy in any density functional approximation. The two constraints are sufficient to remove the self-interaction errors from vrep, correcting its asymptotic behavior at large distances from the system. In the present work, we describe, in complete detail, the constrained minimization method, including recent refinements. We also assess its performance in removing the self-interaction errors for three popular density functional approximations, namely LDA, PBE and B3LYP, by comparing the obtained ionization energies to their experimental values for an extended set of molecules. We show that the results of the constrained minimizations are almost independent of the specific approximation with average percentage errors 15%, 14%, 13% for the above DFAs respectively. These errors are substantially smaller than the corresponding errors of the plain (unconstrained) Kohn-Sham calculations at 38%, 39% and 27% respectively. Finally, we showed that this method correctly predicts negative values for the HOMO energies of several anions.
Τίτλος πηγής δημοσίευσης:	European Physical Journal B
Τόμος/Κεφάλαιο:	91
Τεύχος:	6
Θεματική Κατηγορία:	[EL] Φυσική και θεωρητική χημεία[EN] Physical and theoretical chemistry
Αξιολόγηση από ομότιμους (peer reviewed):	Ναι
Κάτοχος πνευματικών δικαιωμάτων:	© 2018, EDP Sciences, SIF, Springer-Verlag GmbH Germany, part of Springer Nature.
Όροι και προϋποθέσεις δικαιωμάτων:	All Open Access, Green
Σημειώσεις:	Leverhulme Trust: MIS 5002409, RPG-2016-005; European Commission, EC; European Regional Development Fund, FEDER The work was supported by The Leverhulme Trust, through a Research Project Grant with number RPG-2016-005. NNL acknowledges support by the project “Advanced Materials and Devices” (MIS 5002409) implemented under the “Action for the Strategic Development on the Research and Technological Sector”, funded by the Operational Programme “Competitiveness, Entrepreneurship and Innovation” (NSRF 2014-2020) and co-financed by Greece and the European Union (European Regional Development Fund).
Εμφανίζεται στις συλλογές:	Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο