Theoretical and Computational Aspects of the Optimized Effective Potential Approach within Density Functional Theory

Abstract

<p>The computational success of density functional theory relies on the construction of suitable approximations to the exchange-correlation energy functional. Use of functional approximations depending explicitly upon the density alone appear unable to address all aspects of many-body interactions, such as the fundamental constraint that the ground state energy is a piecewise linear function of the total number of electrons, and the ability to model nonlocal effects. Functionals depending explicitly upon occupied and unoccupied Kohn–Sham orbitals are considered necessary to address these and other issues. This dissertation considers certain issues relevant to the successful implementation of explicitly orbital-dependent functionals through the optimized effective potential (OEP) approach, as well as extending the potential functional formalism that provides the formal basis for the OEP approach to systems in the presence of noncollinear magnetic fields.</p><p>The self-consistent implementation of orbital-dependent energy functionals is correctly done through the optimized effective potential approach—minimization of the ground state energy with respect to the Kohn–Sham potential that generates the set of orbitals employed in the energy evaluation. The focus on the potential can be problematic in finite basis set approaches as determining the exchange-correlation potential in this manner is an inverse problem which, depending upon the combination of orbital and potential basis sets employed, is often ill-posed. The ill-posed nature manifests itself as nonphysical exchange-correlation potentials and total energies. We address the problem of determining meaningful exchange-correlation potentials for arbitrary combinations of orbital and potential basis sets through an L-curve regularization approach based on biasing towards smooth potentials in the energy minimization. This approach generates physically reasonable potentials for any combination of basis sets as shown by comparisons with grid-based OEP calculations on atoms, and through direct comparison with DFT calculations employing functionals not depending on orbitals for which OEP can also be performed. This work ensures that the OEP methodology can be considered a viable many-body computational methodology.</p><p>A separate issue of our OEP implementation is that it can suffer from a lack of size-extensivity—the total energy of a system of infinitely separated monomers may not scale linearly with the total number of monomers depending upon how we construct the Kohn–Sham potential. Typically, a fixed reference potential is employed to aid in the convergence of a finite basis set expansion of the Kohn–Sham potential. This reference potential can be utilized to ensure other desirable properties of the resulting potential. In particular, it can enforce the correct asymptotic behavior. The Fermi–Amaldi potential is often used for this purpose but suffers from size-nonextensivity owing to the explicit dependence of the potential on the total number of electrons. This error is examined and shown to be rather small and rapidly approaches a limiting linear behavior. A size-extensive reference potential with the correct asymptotic behavior is suggested and examined.</p><p>We also consider a formal aspect of the potential-based approach that provides the underlying justification of the OEP methodology. The potential functional formalism of Yang, Ayers, and Wu is extended to include systems in the presence of noncollinear magnetic fields. In doing so, a solution to the nonuniqueness issue associated with mapping between potentials and wave functions in such systems is provided, and a computational implementation of the OEP in noncollinear systems is suggested.</p><p>Finally, as an example of an issue for which orbital-dependent functionals seem necessary to obtain a correct description, we consider the ground state structures of C_{4<italic>N</italic> + 2} rings which are believed to exhibit a geometric transition from angle-alternation (<italic>N</italic> ≤ 2) to bond-alternation (<italic>N</italic> > 2). So far, no published DFT approach has been able to reproduce this behavior owing to the tendency of common density functional approximations to bias towards delocalized electron densities. Calculations are presented with the rCAM-B3LYP exchange-correlation functional that correctly predict the structural evolution of this system. This is rationalized in terms of the recently proposed delocalization error for which rCAM-B3LYP explicitly attempts to address.</p>