Spin-dependent gradient correction for more accurate atomization energies of molecules

Abstract

We discuss, simplify, and improve the spin-dependent correction of L.A. Constantin et al., Phys. Rev. B 84, 233103, for atomization energies, and develop a density parameter of the form $v\propto |\nabla n|/n^{10/9}$, 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.

10 pages, 6 figures

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Cited by in corpus (12)

• Thermally-assisted-occupation density functional theory with generalized-gradient approximations
• Laplacian-level kinetic energy approximations based on the fourth-order gradient expansion: Global assessment and application to the subsystem formulation of density functional theory
• Meta-GGA exchange-correlation functional with a balanced treatment of nonlocality
• Semiclassical atom theory applied to solid-state physics
• Assessing the performance of the recent non-empirical semilocal density functionals on describing the lattice constants, bulk moduli and cohesive energies of alkali, alkaline-earth, and transition metals
• Relevance of coordinate and particle-number scaling in density functional theory
• Construction of a general semilocal exchange-correlation hole model: Application to nonempirical meta-GGA functionals
• Gradient-dependent upper bound for the exchange-correlation energy and application to density functional theory
• Generalized gradient approximation correlation energy functionals based on the uniform electron gas with gap model
• Global hybrids from the semiclassical atom theory satisfying the local density linear response
• Spin-dependent gradient correction for more accurate atomization energies of molecules
• Hartree potential dependent exchange functional