Reply to “Comment on ‘Nonanalyticity of the optimized effective potential with finite basis sets’ ”

The Comment by Friedrich et al. does not dispute the central result of our paper [Phys. Rev. A 85, 052508 (2012)] that nonanalytic behavior is present in long-established mathematical pathologies arising in the solution of finite basis optimized effective potential (OEP) equations. In the Comment, the terms “balancing of basis sets” and “basis-set convergence” imply a particular order towards the limit of a large orbital basis sets where the large-orbital-base limit is always taken first, before the large-auxiliary-base limit, until overall convergence is achieved, at a high computational cost. The authors claim that, on physical grounds, this order of limits is not only sufficient, but also necessary in order to avoid the mathematical pathologies. In response to the Comment, we remark that it is already written in our paper that the nonanalyticity trivially disappears with large orbital basis sets. We point out that the authors of the Comment give an incorrect proof of this statement. We also show that the order of limits towards convergence of the potential is immaterial. A recent paper by the authors of the Comment proposes a partial correction for the incomplete orbital basis error in the full-potential linearized augmented-plane-wave method. Similar to the correction developed in our paper, this correction also benefits from an effectively complete orbital basis, even though only a finite orbital basis is employed in the calculation. This shows that it is unnecessary to take, in practice, the limit of an infinite orbital basis in order to avoid mathematical pathologies in the OEP. Our paper is a significant contribution in that direction with general applicability to any choice of basis sets. Finally, contrary to an allusion in the abstract and assertions in the main text of the Comment that unphysical oscillations of the OEP are supposedly attributed to the common energy denominator approximation, in fact, such anomalies arise with the full treatment of the small eigenvalues of the density response function. This characteristic of the finite basis OEP is well known in the literature but also is clearly demonstrated in our paper

Constraining density functional approximations to yield self-interaction free potentials

Self-interactions (SIs) are a major problem in density functional approximations and the source of serious divergence from experimental results. Here, we propose to optimize density functional total energies in terms of the effective local potential, under constraints for the effective potential that guarantee it is free from SI errors and consequently asymptotically correct. More specifically, we constrain the Hartree, exchange and correlation potential to be the electrostatic potential of a non-negative effective repulsive density of N − 1 electrons. In this way, the optimal effective potentials exhibit the correct asymptotic decay, resulting in significantly improved one-electron properties

Calculation of electronic excited states of molecules using the Helmholtz free-energy minimum principle

We show that the Helmholtz free-energy variational principle is the physical principle underlying the ensemble variational theory formulated in seminal papers by Theophilou and by Gross, Oliveira, and Kohn. A method of calculating electronic excitations of atoms and molecules is then proposed, based on the constrained minimization of the free energy. It involves the search for the optimal set of Slater determinant states to describe low electronic excitations and, in a second step, the search for optimal rotations in the space spanned by these states. Boltzmann factors are used as weights of states in the ensemble since for these the free energy achieves a minimum. The proposed method is applied to the Be atom and LiH and BH molecules. The method captures static electron correlation but naturally lacks dynamic correlation. To account for the latter, we describe short-range electron-electron interaction with a density functional, while the long-range part is still expressed by a wave-function method. Using the example of the LiH molecule, we find that the resulting method is able to capture both static and dynamic electron correlations

A local Fock-exchange potential in Kohn–Sham equations

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Orbitals from local RDMFT: Are they Kohn-Sham or Natural Orbitals?

Recently, an approximate theoretical framework was introduced, called local reduced density matrix functional theory (local-RDMFT), where functionals of the one-body reduced density matrix (1-RDM) are minimized under the additional condition that the optimal orbitals satisfy a single electron Schrödinger equation with a local potential. In the present work, we focus on the character of these optimal orbitals. In particular, we compare orbitals obtained by local-RDMFT with those obtained with the full minimization (without the extra condition) by contrasting them against the exact NOs and orbitals from a density functional calculation using the local density approximation (LDA). We find that the orbitals from local-RMDFT are very close to LDA orbitals, contrary to those of the full minimization that resemble the exact NOs. Since local RDMFT preserves the good quality of the description of strong static correlation, this finding opens the way to a mixed density/density matrix scheme, where Kohn-Sham orbitals obtain fractional occupations from a minimization of the occupation numbers using 1-RDM functionals. This will allow for a description of strong correlation at a cost only minimally higher than a density functional calculation

Distinct Magnetic Phase Transition at the Surface of an Antiferromagnet

In the majority of magnetic systems the surface is required to order at the same temperature as the bulk. In the present Letter, we report a distinct and unexpected surface magnetic phase transition at a lower temperature than the Néel temperature. Employing grazing incidence x-ray resonant magnetic scattering, we have observed the near-surface behavior of uranium dioxide. UO2 is a noncollinear, triple-q, antiferromagnet with the U ions on a face-centered cubic lattice. Theoretical investigations establish that at the surface the energy increase—due to the lost bonds—is reduced when the spins near the surface rotate, gradually losing their component normal to the surface. At the surface the lowest-energy spin configuration has a double-q (planar) structure. With increasing temperature, thermal fluctuations saturate the in-plane crystal field anisotropy at the surface, leading to soft excitations that have ferromagnetic XY character and are decoupled from the bulk. The structure factor of a finite two-dimensional XY model fits the experimental data well for several orders of magnitude of the scattered intensity. Our results support a distinct magnetic transition at the surface in the Kosterlitz-Thouless universality class

Thermal Density Functional Theory in Context

This chapter introduces thermal density functional theory, starting from the ground-state theory and assuming a background in quantum mechanics and statistical mechanics. We review the foundations of density functional theory (DFT) by illustrating some of its key reformulations. The basics of DFT for thermal ensembles are explained in this context, as are tools useful for analysis and development of approximations. We close by discussing some key ideas relating thermal DFT and the ground state. This review emphasizes thermal DFT's strengths as a consistent and general framework.Comment: Submitted to Spring Verlag as chapter in "Computational Challenges in Warm Dense Matter", F. Graziani et al. ed

Nonanalyticity of the optimized effective potential with finite basis sets

We show that the finite-basis optimized effective potential (OEP) equations exhibit previously unknown singular behavior. Imposing continuity, we derive new well-behaved finite-basis-set OEP equations that determine OEP for any orbital and any large enough potential basis sets and which adopt an analytic solution via matrix inversion

Electronic non-adiabatic states: towards a density functional theory beyond the Born–Oppenheimer approximation

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