Orbital-dependent Exchange-correlation Functionals Research Articles

Density-functional theory for systems with noncollinear spin: Orbital-dependent exchange-correlation functionals and their application to the Hubbard dimer

A new class of orbital-dependent exchange-correlation (xc) potentials for applications in noncollinear spin-density-functional theory is developed. Starting from the optimized effective potential (OEP) formalism for the exact exchange potential - generalized to the noncollinear case - correlation effects are added via a self-consistent procedure inspired by the Singwi-Tosi-Land-Sjolander (STLS) method. The orbital-dependent xc potentials are applied to the Hubbard dimer in uniform and noncollinear magnetic fields and compared to exact diagonalization and to the Bethe-ansatz local spin-density approximation. The STLS gives the overall best performance for total energies, densities and magnetizations, particularly in the weakly to moderately correlated regime.

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 optimised effective potential (OEP) approach: we consider both the localised Hartree–Fock as well as the Krieger–Li–Iafrate methods. Analysis of density differences at the exchange-only level reveals the impact of the approximations 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.

On the accuracy of frozen density embedding calculations with hybrid and orbital-dependent functionals for non-bonded interaction energies

We analyze the accuracy of the frozen density embedding (FDE) method, with hybrid and orbital-dependent exchange-correlation functionals, for the calculation of the total interaction energies of weakly interacting systems. Our investigation is motivated by the fact that these approaches require, in addition to the non-additive kinetic energy approximation, also approximate non-additive exact-exchange energies. Despite this further approximation, we find that the hybrid/orbital-dependent FDE approaches can reproduce the total energies with the same accuracy (about 1 mHa) as the one of conventional semi-local functionals. In many cases, thanks to error cancellation effects, hybrid/orbital-dependent approaches yield even the smallest error. A detailed energy-decomposition investigation is presented. Finally, the Becke-exchange functional is found to reproduce accurately the non-additive exact-exchange energies also for non-equilibrium geometries. These performances are rationalized in terms of a reduced-gradient decomposition of the non-additive exchange energy.

Optimized effective potential for calculations with orbital-free potential functionals

Approximation of electronic kinetic energy can be naturally expressed in terms of the one-electron effective potential, namely as a potential functional. Such approximate functionals can lead to linear scaling orbital-free calculations of large systems. For calculation within orbital-free potential functionals, a new optimized effective potential (OEP) method has been developed presently for the direct optimization of electronic ground state energy. This approach parallels the development of OEP for the direct optimization of orbital-dependent exchange-correlation functionals within the Kohn–Sham density functional theory (DFT) framework. It uses the effective one-electron potential as the basic computation variable. This potential is further expanded as a linear combination of basis functions plus a fixed reference potential. Thus, the potential optimization is transformed into the optimization of linear coefficients associated with the basis sets. As a key quantity within the orbital-free potential functionals, the chemical potential controls the correct number of electrons and depends on the trial one-electron potential. The derivatives of the chemical potential with respect to the potential variations have been derived and their use leads to a very efficient electron-number conserving update of the trial potential. The calculations of several atoms and diatomic molecules with the simple Thomas–Fermi–Dirac approximate functional has been carried out to demonstrate our approach. The developed OEP approach should be an efficient computational tool for orbital-free potential functionals.

Unambiguous optimization of effective potentials in finite basis sets

The optimization of effective potentials is of interest in density-functional theory (DFT) in two closely related contexts. First, the evaluation of the functional derivative of orbital-dependent exchange-correlation functionals requires the application of optimized effective potential methods. Second, the optimization of the effective local potential that yields a given electron density is important both for the development of improved approximate functionals and for the practical application of embedding schemes based on DFT. However, in all cases this optimization turns into an ill-posed problem if a finite basis set is introduced for the Kohn-Sham orbitals. So far, this problem has not been solved satisfactorily. Here, a new approach to overcome the ill-posed nature of such finite-basis set methods is presented for the optimization of the effective local potential that yields a given electron density. This new scheme can be applied with orbital basis sets of reasonable size and makes it possible to vary the basis sets for the orbitals and for the potential independently, while providing an unambiguous potential that systematically approaches the numerical reference.

Adaptation of the projector-augmented-wave formalism to the treatment of orbital-dependent exchange-correlation functionals

ochl [Phys. Rev. B 50 17953 (1994)] for electronic structure calculations. The methodology is illustrated with binding energy curves for C in the diamond structure and LiF in the rock salt structure, comparing results from the Hartree-Fock (HF) formalism and the Optimized Effective Potential (OEP) formalism in the so-called KLI approximation [Krieger, Li, and Iafrate, Phys. Rev. A 45, 101 (1992)] with those of the local density approximation (LDA). While the work here uses pure Fock exchange only, the formalism can be extended to treat orbital-dependent functionals more generally.

Progress at the interface of wave-function and density-functional theories

The Kohn-Sham (KS) potential of density-functional theory (DFT) emerges as the minimizing effective potential in a variational scheme that does not involve fixing the unknown single-electron density. Using Rayleigh Schr\"odinger (RS) perturbation theory (PT), we construct ab initio approximations for the energy difference, the minimization of which determines the KS potential directly---thereby bypassing DFT's traditional algorithm to search for the density that minimizes the total energy. From second-order RS PT, we obtain variationally stable energy differences to be minimized, solving the severe problem of variational collapse of orbital-dependent exchange-correlation functionals based on second-order RS PT.

Ab initio DFT – the seamless connection between WFT and DFT

Orbital-dependent exchange-correlation functionals and potentials play an increasingly important role in Density Functional Theory (DFT). Methods which use explicit orbital-dependent functionals can be viewed as a natural extension to the standard Kohn–Sham (KS) procedure in DFT, that traditionally have used functionals with explicit density-dependence but only implicit orbital-dependence. Ab initio DFT, invented at the Quantum Theory Project, is the method which could define rigorous orbital-dependent exchange-correlation functionals and potentials in the context of KS DFT theory. The local and multiplicative exchange-correlation potentials are derived from a general theoretical framework based on the density condition in KS theory and from coupled-cluster theory and many-body perturbation theory. Ab initio DFT guarantees to converge to the right answer in the correlation and basis set limit, just as does ab initio Wave Function Theory (WFT) and solves in a rigorous way most of the shortcomings of standard density-dependent KS DFT. It is also the route toward understanding the relationships between traditional ab initio WFT and DFT. The Optimized Effective Potential ‘journey’ on the borderline of WFT and DFT was inspired and possible only because of the Quantum Theory Project where we stayed as postdocs in 1999–2001. It seems to us then we were in the right place and at the right time, and certainly with the right people. The QTP scientific melting pot and Sanibel's meetings gave us an excellent possibility to work together, learn and hopefully solve many important scientific problems.

Density-Functional Theory with Orbital-Dependent Functionals: Exact-exchange Kohn-Sham and Density-Functional Response Methods

Abstract Kohn-Sham methods with orbital-dependent exchange-correlation functionals, in particular exact-exchange methods, are discussed. The numerical stability of optimized-effective-potential methods to construct the exchange-correlation potential in the case of orbital-dependent energy functionals is considered. A numerically stable exact-exchange Kohn-Sham method is briefly presented. A new ansatz for time-dependent density-functional methods in the response regime is considered and an exact-exchange time-dependent density-functional method based on it is discussed and it is demonstrated that this methods is able to treat qualitatively correctly charge-transfer excitations.

Numerically stable optimized effective potential method with balanced Gaussian basis sets

A solution to the long-standing problem of developing numerically stable optimized effective potential (OEP) methods based on Gaussian basis sets is presented by introducing an approach consisting of an exact exchange OEP method with an accompanying construction and balancing scheme for the involved auxiliary and orbital Gaussian basis sets that is numerically stable and that properly represents an exact exchange Kohn-Sham method. The method is a purely analytical method that does not require any numerical grid, scales like Hartree-Fock or B3LYP procedures, is straightforward to implement, and is easily generalized to take into account orbital-dependent density functionals other than the exact exchange considered in this work. Thus, the presented OEP approach opens the way to the development and application of novel orbital-dependent exchange-correlation functionals. It is shown that adequately taking into account the continuum part of the Kohn-Sham orbital spectrum is crucial for numerically stable Gaussian basis set OEP methods. Moreover, it is mandatory to employ orbital basis sets that are converged with respect to the used auxiliary basis representing the exchange potential. OEP calculations in the past often did not meet the latter requirement and therefore may have led to erroneously low total energies.

Ab initio correlation functionals from second-order perturbation theory

Orbital-dependent exchange-correlation functionals are not limited by the explicit dependence on the density and present an attractive alternative to conventional functionals. With the successful implementation of the exact orbital-dependent exchange functional, the challenge lies in developing orbital-dependent approximations for the correlation functional. Ab initio many-body methods can provide such approximations. In particular, perturbation theory with the Kohn-Sham model as the reference [Görling and Levy, Phys. Rev. A 50, 196 (1994)] defines the exact correlation functional via an infinite perturbation series. The second-order term of these series gives the lowest-order approximation to the correlation functional. However, it has been suggested [Bartlett et al., J. Chem. Phys. 122, 034104 (2005)] that the Kohn-Sham Hamiltonian is not the optimal choice for the perturbation expansion and a different reference Hamiltonian may lead to an improved perturbation series and more accurate second-order approximation. Here, we demonstrate explicitly that the modified series can be used to define superior functional and potential. We present results of atomic and molecular calculations with both second-order functionals. Our results demonstrate that the modified functional offers a significantly improved description of the correlation effects as it does not suffer from convergence problems and results in energies and densities that are more accurate than those obtained with second-order Møller-Plesset perturbation theory or generalized-gradient approximation functionals.

Away from generalized gradient approximation: Orbital-dependent exchange-correlation functionals

The local-density approximation of density functional theory (DFT) is remarkably accurate, for instance, for geometries and frequencies, and the generalized gradient approximations have also made bond energies quite reliable. Sometimes, however, one meets with failure in individual cases. One of the possible routes towards better functionals would be the incorporation of orbital dependence (which is an implicit density dependency) in the functionals. We discuss this approach both for energies and for response properties. One possibility is the use of the Hartree-Fock-type exchange energy expression as orbital-dependent functional. We will argue that in spite of the increasing popularity of this approach, it does not offer any advantage over Hartree-Fock for energies. We will advocate not to apply the separation of exchange and correlation, which is so ingrained in quantum chemistry, but to model both simultaneously. For response properties the energies and shapes of the virtual orbitals are crucial. We will discuss the benefits that Kohn-Sham potentials can offer which are derived from either an orbital-dependent energy functional, including the exact-exchange functional, or which can be obtained directly as orbital-dependent functional. We highlight the similarity of the Hartree-Fock and Kohn-Sham occupied orbitals and orbital energies, and the essentially different meanings the virtual orbitals and orbital energies have in these two models. We will show that these differences are beneficial for DFT in the case of localized excitations (in a small molecule or in a fragment), but are detrimental for charge-transfer excitations. Again, orbital dependency, in this case in the exchange-correlation kernel, offers a solution.

Pseudopotentials from orbital-dependent exchange-correlation functionals

Norm-conserving pseudopotentials are generated on the basis of the optimized potential method ~OPM!, combining the exact exchange with two different correlation functionals, i.e., the orbital-dependent form of Colle and Salvetti ~CS! @Theor. Chim. Acta 37, 329 ~1975!# and the local density approximation ~LDA!. Application of both types of OPM pseudopotentials to a number of diatomic molecules leads to substantially different predictions for spectroscopic constants, thus indicating the importance of a suitable choice for the correlation functional to be used in the OPM context. Moreover, while the CS values are closer to the experimental data, our results nevertheless indicate that a really adequate correlation functional for use with the exact exchange is not yet available. In any case, both variants of the OPM-based pseudopotentials show an improved transferability compared with standard LDA pseudopotentials. @S1050-2947~98!03811-6#