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E. Fabiano

Publications and source records attributed to E. Fabiano.

36 records · Page 2Linked to original sources
arXiv2015

Gradient-dependent upper bound for the exchange-correlation energy and application to density functional theory

We propose a simple gradient-dependent bound for the exchange-correlation energy (sLL), based on the recent non-local bound derived by Lewin and Lieb. We show that sLL is equivalent to the original Lieb-Oxford bound in rapidly-varying density cases but it is tighter for slowly-varying density systems. To show the utility of the sLL bound we apply it to the construction of simple semilocal and non-local exchange and correlation functionals. In both cases improved results, with respect to the use of Lieb-Oxford bound, are obtained showing the power of the sLL bound.

cond-mat.other↗
arXiv2015

Global hybrids from the semiclassical atom theory satisfying the local density linear response

We propose global hybrid approximations of the exchange-correlation (XC) energy functional which reproduce well the modified fourth-order gradient expansion of the exchange energy in the semiclassical limit of many-electron neutral atoms and recover the full local density approximation (LDA) linear response. These XC functionals represent the hybrid versions of the APBE functional [Phys. Rev. Lett. 106, 186406, (2011)] yet employing an additional correlation functional which uses the localization concept of the correlation energy density to improve the compatibility with the Hartree-Fock exchange as well as the coupling-constant-resolved XC potential energy. Broad energetical and structural testings, including thermochemistry and geometry, transition metal complexes, non-covalent interactions, gold clusters and small gold-molecule interfaces, as well as an analysis of the hybrid parameters, show that our construction is quite robust. In particular, our testing shows that the resulting hybrid, including 20\% of Hartree-Fock exchange and named hAPBE, performs remarkably well for a broad palette of systems and properties, being generally better than popular hybrids (PBE0 and B3LYP). Semi-empirical dispersion corrections are also provided.

physics.chem-ph↗
arXiv2014

Kohn-Sham Kinetic Energy Density in the Nuclear and Asymptotic Regions: Deviations from the Von Weizsäcker Behavior and Applications to Density Functionals

We show that the Kohn-Sham positive-definite kinetic energy (KE) density significantly differs from the von Weizsäcker (VW) one at the nuclear cusp as well as in the asymptotic region. At the nuclear cusp, the VW functional is shown to be linear and the contribution of p-type orbitals to the KE density is theoretically derived and numerically demonstrated in the limit of infinite nuclear charge, as well in the semiclassical limit of neutral large atoms. In the latter case, it reaches 12 of the KE density. In the asymptotic region we find new exact constraints for meta Generalized Gradient Approximation (meta-GGA) exchange functionals: with an exchange enhancement factor proportional to $\sqrtα$, where $α$ is the common meta-GGA ingredient, both the exchange energy density and the potential are proportional to the exact ones. In addition, this describes exactly the large-gradient limit of quasi-two dimensional systems.

physics.chem-ph↗
arXiv2014

Orbital-dependent second-order scaled-opposite-spin correlation functionals in the optimized effective potential method

The performance of correlated optimized effective potential (OEP) functionals based on the spin-resolved second-order correlation energy is analyzed. The relative importance of singly- and doubly- excited contributions as well as the effect of scaling the same- and opposite- spin components is investigated in detail comparing OEP results with Kohn-Sham (KS) quantities determined via an inversion procedure using accurate ab initio electronic densities. Special attention is dedicated in particular to the recently proposed scaled-opposite-spin OEP functional [I. Grabowski, E. Fabiano and F. Della Sala, Phys. Rev. B, 87, 075103, (2013)] which is the most advantageous from a computational point of view. We find that for high accuracy a careful, system dependent, selection of the scaling coefficient is required. We analyze several size-extensive approaches for this selection. Finally, we find that a composite approach, named OEP2-SOSh, based on a post-SCF rescaling of the correlation energy can yield high accuracy for many properties, being comparable with the most accurate OEP procedures previously reported in the literature but at substantially reduced computational effort.

physics.chem-ph↗
arXiv2014

Wave-function and density functional theory studies of dihydrogen complexes

We performed a benchmark study on a series of dihydrogen bond complexes and constructed a set of reference bond distances and interaction energies. The test set was employed to assess the performance of several wave-function correlated and density functional theory methods. We found that second-order correlation methods describe relatively well the dihydrogen complexes. However, for high accuracy inclusion of triple contributions is important. On the other hand, none of the considered density functional methods can simultaneously yield accurate bond lengths and interaction energies. However, we found that improved results can be obtained by the inclusion of non-local exchange contributions.

physics.chem-ph↗
arXiv2014

Generalized gradient approximation correlation energy functionals based on the uniform electron gas with gap model

We study the uniform electron gas with a gap model in the context of density functional theory. Based on this analysis, we construct two local gap models that realize generalized gradient approximation (GGA) correlation functionals satisfying numerous exact constraints for the correlation energy. The first one, named GAPc, fulfills the full second-order correlation gradient expansion at any density regime, is very accurate for jellium surfaces, comparable to state-of-the-art GGAs for atomic systems and molecular systems, and well compatible with known semilocal exchange. The second functional, named GAPloc, is satisfying the same exact conditions, except that the second-order gradient expansion is sacrificed for a better behavior under the Thomas-Fermi scaling and a more realistic correlation energy density of the hellium atom. The GAPloc functional displays a high accuracy for atomic correlation energies, still preserving a reasonable behavior for jellium surfaces. Moreover, it shows a higher compatibility with the Hartree-Fock exchange than other semilocal correlation functionals. This feature is explained in terms of the real-space analysis of the GAPloc correlation energy.

cond-mat.other↗
arXiv2014

Laplacian-level kinetic energy approximations based on the fourth-order gradient expansion: Global assessment and application to the subsystem formulation of density functional theory

We test Laplacian-level meta-generalized gradient approximation (meta-GGA) non-interacting kinetic energy functionals based on the fourth-order gradient expansion (GE4). We consider several well known Laplacian-level meta-GGAs from literature (bare GE4, modified GE4, and the MGGA functional of Perdew and Constantin [Phys. Rev. B \textbf{75},155109 (2007)]), as well as two newly designed Laplacian-level kinetic energy functionals (named L0.4 and L0.6). First, a general assessment of the different functionals is performed, testing them for model systems (one-electron densities, Hooke's atom and different jellium systems), atomic and molecular kinetic energies as well as for their behavior with respect to density-scaling transformations. Finally, we assess, for the first time, the performance of the different functionals for Subsystem Density Functional Theory (DFT) calculations on non-covalently interacting systems. We find that the different Laplacian-level meta-GGA kinetic functionals may improve the description of different properties of electronic systems but no clear overall advantage is found over the best GGA functionals. Concerning Subsystem DFT calculations, the here proposed L0.4 kinetic energy functional is competitive with state-of-the-art GGAs, whereas all other Laplacian-level functionals fail badly. The performance of the Laplacian-level functionals is rationalized thanks to a two-dimensional reduced-gradient and reduced-Laplacian decomposition of the non-additive kinetic energy density.

physics.chem-ph↗
arXiv2014

Frozen density embedding with non-integer subsystems' particle numbers

We extend the frozen density embedding theory to non-integer subsystems' particles numbers. Different features of this formulation are discussed, with special concern for approximate embedding calculations. In particular, we highlight the relation between the non-integer particle-number partition scheme and the resulting embedding errors. Finally, we provide a discussion of the implications of the present theory for the derivative discontinuity issue and the calculation of chemical reactivity descriptors.

physics.chem-ph↗
arXiv2013

A Density Difference Based Analysis of Orbital--Dependent Exchange--Correlation Functionals

We present a density difference based analysis for a range of orbital--dependent Kohn--Sham functionals. Results for atoms, some members of the neon isoelectronic series and small molecules are reported and compared with ab initio wave-function calculations. Particular attention is paid to the quality of approximations to the exchange--only optimized effective potential (OEP) approach: we consider both the Localized Hartree Fock as well as the Krieger-Li-Iafrate methods. Analysis of density differences at the exchange--only level reveals the impact the approximations have on the resulting electronic densities. These differences are further quantified in terms of the ground state energies, frontier orbital energy differences and highest occupied orbital energies obtained. At the correlated level an OEP approach based on a perturbative second--order correlation energy expression is shown to deliver results comparable with those from traditional wave function approaches, making it suitable for use as a benchmark against which to compare standard density--functional approximations.

physics.chem-ph↗
arXiv2013

Construction of a general semilocal exchange-correlation hole model: Application to nonempirical meta-GGA functionals

Using a reverse-engineering method we construct a meta-generalized gradient approximation (meta-GGA) angle-averaged exchange-correlation hole model which has a general applicability. It satisfies known exact hole constraints and can exactly recover the exchange-correlation energy density of any reasonable meta-GGA exchange-correlation energy functional satisfying a minimal set of exact properties. The hole model is applied to several non-empirical meta-GGA functionals: the Tao-Perdew-Staroverov-Scuseria (TPSS), the revised TPSS (revTPSS) and the recently Balanced LOCalization (BLOC) meta-GGA of L.A. Constantin, E. Fabiano, and F. Della Sala, (J. Chem. Theory Comput. 9, 2256 (2013)). The empirical M06-L meta-GGA functional is also considered. Real-space analyses of atoms and ions as well as wave-vector analyses of jellium surface energies, show that the meta-GGA hole models, in particular the BLOC one, are very realistic and can reproduce many features of benchmark XC holes. In addition, the BLOC hole model can be used to estimate with good accuracy the Coulomb hole radius of small atoms and ions. Thus, the proposed meta-GGA hole models provide a valuable tool to validate in detail existing meta-GGA functionals, and can be further used in the development of DFT methods beyond the semilocal level of theory.

physics.chem-ph↗
arXiv2013

Simple non-empirical procedure for spin-component-scaled MP2 methods applied to the calculation of dissociation energy curve of noncovalently-interacting systems

We present a simple and non-empirical method to determine optimal scaling coefficients, within the (spin-component)-scaled MP2 approach, for calculating intermolecular potential energies of noncovalently-interacting systems. The method is based on an observed proportionality between (spin-component) MP2 and CCSD(T) energies for a wide range of intermolecular distances and allows to compute with high accuracy a large portion of the dissociation curve at the cost of a single CCSD(T) calculation. The accuracy of the present procedure is assessed for a series of noncovalently-interacting test systems: the obtained results reproduce CCSD(T) quality in all cases and definitely outperform conventional MP2, CCSD and SCS-MP2 results. The difficult case of the Beryllium dimer is also considered.

physics.chem-ph↗
arXiv2013

Meta-GGA exchange-correlation functional with a balanced treatment of nonlocality

We construct a meta-generalized-gradient approximation which properly balances the nonlocality contributions to the exchange and correlation at the semilocal level. This non-empirical functional shows good accuracy for a broad palette of properties (thermochemistry, structural properties) and systems (molecules, metal clusters, surfaces and bulk solids). The accuracy for several well known problems in electronic structure calculations, such as the bending potential of the silver trimer and the dimensional crossover of anionic gold clusters, is also demonstrated. The inclusion of empirical dispersion corrections is finally discussed and analyzed.

physics.chem-ph↗
arXiv2013

Semilocal and Hybrid Density Embedding Calculations of Ground-State Charge-Transfer Complexes

We apply the frozen density embedding method, using a full relaxation of embedded densities through a freeze-and-thaw procedure, to study the electronic structure of several benchmark ground-state charge-transfer complexes, in order to assess the merits and limitations of the approach for this class of systems. The calculations are performed using both semilocal and hybrid exchange-correlation (XC) functionals. The results show that embedding calculations using semilocal XC functionals yield rather large deviations with respect to the corresponding supermolecular calculations. Due to a large error cancellation effect, however, they can often provide a relatively good description of the electronic structure of charge-transfer complexes, in contrast to supermolecular calculations performed at the same level of theory. On the contrary, when hybrid XC functionals are employed, both embedding and supermolecular calculations agree very well with each other and with the reference benchmark results. In conclusion, for the study of ground-state charge-transfer complexes via embedding calculations hybrid XC functionals are the method of choice due to their higher reliability and superior performance.

physics.chem-ph↗
arXiv2013

Accuracy of basis-set extrapolation schemes for DFT-RPA correlation energies in molecular calculations

We construct a reference benchmark set for atomic and molecular random-phase-approximation (RPA) correlation energies in a density functional theory (DFT) framework at the complete basis set limit. This set is used to evaluate the accuracy of some popular extrapolation schemes for RPA all-electron molecular calculations. The results indicate that for absolute energies accurate results, clearly outperforming raw data, are achievable with two-point extrapolation schemes based on quintuple- and sextuple-zeta basis sets. Moreover, we show that results in good agreement with the benchmark can also be also obtained by using a semiempirical extrapolation procedure based on quadruple- and quintuple-zeta basis sets. Finally, we analyze the performance of different extrapolation schemes for atomization energies.

physics.chem-ph↗
arXiv2013

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

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.

physics.chem-ph↗
arXiv2013

Testing the broad applicability of the PBEint GGA functional and its one-parameter hybrid form

We review the performance of the PBEint GGA functional (Phys. Rev. B 2010, 82, 113104) recently proposed to improve the description of hybrid interfaces, and we introduce its one-parameter hybrid form (hPBEint). We consider different well established benchmarks for energetic and structural properties of molecular and solid-state systems as well as model systems and newly developed benchmark sets for dipole moments and metal-molecule interactions. We find that PBEint and hPBEint (with 16.67% Hartree-Fock exchange) yield the overall best performance, working well for most of the considered properties and systems and showing a balanced behavior for different problems. In particular, due to their well-balanced accuracy, they perform well for the description of hybrid metal-molecule interfaces.

physics.chem-ph↗
arXiv2002

Phonons and gluons in the crystalline color superconducting phase of QCD

The High Density Effective Theory formalism is used to calculate the low energy properties of the phonons and gluons in the Larkin-Ovchinnikov-Fulde-Ferrell (LOFF) phase of two-flavor QCD. The effective phonon Lagrangian for the cubic crystal structure, which is favored according to a recent study, depends, at the second order in the derivatives, on three parameters which we calculate in this paper. We also compute for soft momenta the effective lagrangian for the gluons of the unbroken SU(2)_c group, both for a single plane wave structure and for the cube. In both cases the Meissner gluon mass vanishes as in the case of complete isotropy; on the other hand there is a partial Debye screening due to the existence of blocking regions on the Fermi spheres. For the single plane wave structure the gluon dielectric tensor is non isotropic, while it is isotropic for the cubic crystal, in spite of the intrinsic anisotropy of the structure.

hep-ph↗