Comment on "Modifying the variational principle in the action integral functional derivation of time-dependent density functional theory" by Jochen Schirmer [arXiv:1010.4223]

In a paper recently published in Phys. Rev. A [arXiv:1010.4223], Schirmer has criticized an earlier work of mine [arXiv:0803.2727], as well as the foundations of time-dependent density functional theory. In Ref.[2], I showed that the so-called "causality paradox" - i.e., the failure of the exchange-correlation potential derived from the Runge-Gross time-dependent variational principle to satisfy causality requirements - can be solved by a careful reformulation of that variational principle. Fortunately, the criticism presented in Ref.[1] is based on elementary misunderstandings of the nature of functionals, gauge transformations, and the time-dependent variational principle. In this Comment I wish to point out and clear these misunderstandings.Comment: 4 pages. Accepted for publication in Phys. Rev.

Voltage-Controlled Surface Magnetization of Itinerant Ferromagnet Ni_(1-x)Cu_x

We argue that surface magnetization of a metallic ferromagnet can be turned on and off isothermally by an applied voltage. For this, the material's electron subsystem must be close enough to the boundary between para- and ferromagnetic regions on the electron density scale. For the 3d series, the boundary is between Ni and Cu, which makes their alloy a primary candidate. Using Ginzburg-Landau functional, which we build from Ni_(1-x)Cu_x empirical properties, ab-initio parameters of Ni and Cu, and orbital-free LSDA, we show that the proposed effect is experimentally observable.Comment: 4 pages; 2 figures; submitted to PRL February 16th 2008; transferred to PRB June 21st 2008; published July 15th 200

Closed-form expressions for correlated density matrices: application to dispersive interactions and example of (He)2

Empirically correlated density matrices of N-electron systems are investigated. Exact closed-form expressions are derived for the one- and two-electron reduced density matrices from a general pairwise correlated wave function. Approximate expressions are proposed which reflect dispersive interactions between closed-shell centro-symmetric subsystems. Said expressions clearly illustrate the consequences of second-order correlation effects on the reduced density matrices. Application is made to a simple example: the (He)2 system. Reduced density matrices are explicitly calculated, correct to second order in correlation, and compared with approximations of independent electrons and independent electron pairs. The models proposed allow for variational calculations of interaction energies and equilibrium distance as well as a clear interpretation of dispersive effects on electron distributions. Both exchange and second order correlation effects are shown to play a critical role on the quality of the results.Comment: 22 page

Hole polaron formation and migration in olivine phosphate materials

By combining first principles calculations and experimental XPS measurements, we investigate the electronic structure of potential Li-ion battery cathode materials LiMPO4 (M=Mn,Fe,Co,Ni) to uncover the underlying mechanisms that determine small hole polaron formation and migration. We show that small hole polaron formation depends on features in the electronic structure near the valence-band maximum and that, calculationally, these features depend on the methodology chosen for dealing with the correlated nature of the transition-metal d-derived states in these systems. Comparison with experiment reveals that a hybrid functional approach is superior to GGA+U in correctly reproducing the XPS spectra. Using this approach we find that LiNiPO4 cannot support small hole polarons, but that the other three compounds can. The migration barrier is determined mainly by the strong or weak bonding nature of the states at the top of the valence band, resulting in a substantially higher barrier for LiMnPO4 than for LiCoPO4 or LiFePO4

Interactions and Broken Time-Reversal Symmetry in Chaotic Quantum Dots

When treating interactions in quantum dots within a RPA-like approach, time-reversal symmetry plays an important role as higher-order terms -- the Cooper series -- need to be included when this symmetry is present. Here we consider model quantum dots in a magnetic field weak enough to leave the dynamics of the dot chaotic, but strong enough to break time-reversal symmetry. The ground state spin and addition energy for dots containing 120 to 200 electrons are found using local spin density functional theory, and we compare the corresponding distributions with those derived from an RPA-like treatment of the interactions. The agreement between the two approaches is very good, significantly better than for analogous calculations in the presence of time-reversal symmetry. This demonstrates that the discrepancies between the two approaches in the time-reversal symmetric case indeed originate from the Cooper channel, indicating that these higher-order terms might not be properly taken into account in the spin density functional calculations.Comment: 4 pages, 3 figure

Ground state of two electrons on concentric spheres

We extend our analysis of two electrons on a sphere [Phys. Rev. A {\bf 79}, 062517 (2009); Phys. Rev. Lett. {\bf 103}, 123008 (2009)] to electrons on concentric spheres with different radii. The strengths and weaknesses of several electronic structure models are analyzed, ranging from the mean-field approximation (restricted and unrestricted Hartree-Fock solutions) to configuration interaction expansion, leading to near-exact wave functions and energies. The M{\o}ller-Plesset energy corrections (up to third-order) and the asymptotic expansion for the large-spheres regime are also considered. We also study the position intracules derived from approximate and exact wave functions. We find evidence for the existence of a long-range Coulomb hole in the large-spheres regime, and infer that unrestricted Hartree-Fock theory over-localizes the electrons.Comment: 10 pages, 10 figure