We discuss, simplify, and improve the spin-dependent correction of Constantin et al. [Phys. Rev. B 84, 233103 (2011) https://doi.org/10.1103/PhysRevB.84.233103] for atomization energies, and develop a density parameter of the form v∝|∇n|/n10/9, found from the statistical ensemble of one-electron densities. The here constructed exchange-correlation generalized gradient approximations (GGAs), named zvPBEsol and zvPBEint, show a broad applicability, and a good accuracy for many applications, because these corrected functionals significantly improve the atomization and binding energies of molecular systems, without worsening the behavior of the original functionals (PBEsol and PBEint) for other properties. This spin-dependent correction is also applied to meta-GGA dynamical correlation functionals combined with exact-exchange; in this case a significant (about 30%) improvement in atomization energies of small molecules is found.
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21 November 2012
Research Article|
November 21 2012
Spin-dependent gradient correction for more accurate atomization energies of molecules
Lucian A. Constantin;
Lucian A. Constantin
1Center for Biomolecular Nanotechnologies @UNILE,
Istituto Italiano di Tecnologia (IIT)
, Via Barsanti, 73010 Arnesano (LE), Italy
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Eduardo Fabiano;
Eduardo Fabiano
2National Nanotechnology Laboratory (NNL),
Istituto Nanoscienze-CNR
, Via per Arnesano 16, I-73100 Lecce, Italy
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Fabio Della Sala
Fabio Della Sala
1Center for Biomolecular Nanotechnologies @UNILE,
Istituto Italiano di Tecnologia (IIT)
, Via Barsanti, 73010 Arnesano (LE), Italy
2National Nanotechnology Laboratory (NNL),
Istituto Nanoscienze-CNR
, Via per Arnesano 16, I-73100 Lecce, Italy
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J. Chem. Phys. 137, 194105 (2012)
Article history
Received:
July 17 2012
Accepted:
October 23 2012
Citation
Lucian A. Constantin, Eduardo Fabiano, Fabio Della Sala; Spin-dependent gradient correction for more accurate atomization energies of molecules. J. Chem. Phys. 21 November 2012; 137 (19): 194105. https://doi.org/10.1063/1.4766324
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