Undoing static correlation: Long-range charge transfer in time-dependent density functional theory

Long-range charge transfer excited states are notoriously badly underestimated in time-dependent density functional theory (TDDFT). We resolve how {\it exact} TDDFT captures charge transfer between open-shell species: in particular the role of the step in the ground-state potential, and the severe frequency-dependence of the exchange-correlation kernel. An expression for the latter is derived, that becomes exact in the limit that the charge-transfer excitations are well-separated from other excitations. The exchange-correlation kernel has the task of undoing the static correlation in the ground state introduced by the step, in order to accurately recover the physical charge-transfer states.Comment: 2 figure

Novel properties of the Kohn-Sham exchange potential for open systems: application to the two-dimensional electron gas

The properties of the Kohn-Sham (KS) exchange potential for open systems in thermodynamical equilibrium, where the number of particles is non-conserved, are analyzed with the Optimized Effective Potential (OEP) method of Density Functional Theory (DFT) at zero temperature. The quasi two-dimensional electron gas (2DEG) is used as an illustrative example. The main findings are that the KS exchange potential builds a significant barrier-like structure under slight population of the second subband, and that both the asymptotic value of the KS exchange potential and the inter-subband energy jump discontinuously at the one-subband (1S) -> two-subband (2S) transition. The results obtained in this system offer new insights on open problems of semiconductors, such as the band-gap underestimation and the band-gap renormalization by photo-excited carriers.Comment: 7 pages, 3 figures, uses epl.cls(included), accepted for publication in Europhysics Letter

A Paradigm of Translational Medicine

Antimicrobial peptides (AMPs) are small, cationic, amphiphilic peptides with broad-spectrum microbicidal activity against both bacteria and fungi. In mammals, AMPs form the first line of host defense against infections and generally play an important role as effector agents of the innate immune system. The AMP era was born more than 6 decades ago when the first cationic cyclic peptide antibiotics, namely polymyxins and tyrothricin, found their way into clinical use. Due to the good clinical experience in the treatment of, for example, infections of mucus membranes as well as the subsequent understanding of mode of action, AMPs are now considered for treatment of inflammatory skin diseases and for improving healing of infected wounds. Based on the preclinical findings, including pathobiochemistry and molecular medicine, targeted therapy strategies are developed and first results indicate that AMPs influence processes of diseased skin. Importantly, in contrast to other antibiotics, AMPs do not seem to propagate the development of antibiotic-resistant micro-organisms. Therefore, AMPs should be tested in clinical trials for their efficacy and tolerability in inflammatory skin diseases and chronic wounds. Apart from possible fields of application, these peptides appear suited as an example of the paradigm of translational medicine for skin diseases which is today seen as a ‘two-way road’ – from bench to bedside and backwards from bedside to bench

Becke-Johnson-type exchange potential for two-dimensional systems

We extend the Becke-Johnson approximation [J. Chem. Phys. 124, 221101 (2006)] of the exchange potential to two dimensions. We prove and demonstrate that a direct extension of the underlying formalism may lead to divergent behavior of the potential. We derive a cure to the approach by enforcing the gauge invariance and correct asymptotic behavior of the exchange potential. The procedure leads to an approximation which is shown, in various quasi-two-dimensional test systems, to be very accurate in comparison with the exact exchange potential, and thus a considerable improvement over the commonly applied local-density approximation.Comment: submitted to Phys. Rev. B on July 9th, 200

Violation of the `Zero-Force Theorem' in the time-dependent Krieger-Li-Iafrate approximation

We demonstrate that the time-dependent Krieger-Li-Iafrate approximation in combination with the exchange-only functional violates the `Zero-Force Theorem'. By analyzing the time-dependent dipole moment of Na5 and Na9+, we furthermore show that this can lead to an unphysical self-excitation of the system depending on the system properties and the excitation strength. Analytical aspects, especially the connection between the `Zero-Force Theorem' and the `Generalized-Translation Invariance' of the potential, are discussed.Comment: 5 pages, 4 figure

Orbital densities functional

Local density approximation (LDA) to the density functional theory (DFT) has continuous derivative of total energy as a number of electrons function and continuous exchange-correlation potential, while in exact DFT both should be discontinuous as number of electrons goes through an integer value. We propose orbital densities functional (ODF) (with orbitals defined as Wannier functions) that by construction obeys this discontinuity condition. By its variation one-electron equations are obtained with potential in the form of projection operator. The operator increases a separation between occupied and empty bands thus curing LDA deficiency of energy gap value systematic underestimation. Orbital densities functional minimization gives ground state orbital and total electron densities. The ODF expression for the energy of orbital densities fluctuations around the ground state values defines ODF fluctuation Hamiltonian that allows to treat correlation effects. Dynamical mean-field theory (DMFT) was used to solve this Hamiltonian with quantum Monte Carlo (QMC) method for effective impurity problem. We have applied ODF method to the problem of metal-insulator transition in lanthanum trihydride LaH_{3-x}. In LDA calculations ground state of this material is metallic for all values of hydrogen nonstoichiometry x while experimentally the system is insulating for x < 0.3. ODF method gave paramagnetic insulator solution for LaH_3 and LaH_{2.75} but metallic state for LaH_{2.5}.Comment: 35 pages, 5 figure

Exact-exchange Kohn-Sham potential, surface energy, and work function of jellium slabs

Exact-exchange self-consistent calculations of the Kohn-Sham potential, surface energy, and work function of jellium slabs are reported in the framework of the Optimized Effective Potential (OEP) scheme of Density Functional Theory. In the vacuum side of the jellium surface and at a distance $z$ that is larger than the slab thickness, the exchange-only Kohn-Sham potential is found to be image-like ($\sim -e^2/z$) but with a coefficient that differs from that of the classical image potential $V_{im}(z)=-e^2/4z$. The three OEP contributions to the surface energy (kinetic, electrostatic, and exchange) are found to oscillate as a function of the slab thickness, as occurs in the case of the corresponding calculations based on the use of single-particle orbitals and energies obtained in the Local Density Approximation (LDA). The OEP work function presents large quantum size effects that are absent in the LDA and which reflect the intrinsic derivative discontinuity of the exact Kohn-Sham potential.Comment: 25 pages, 9 figures, to appear in Phys. Rev.

Parameterized optimized effective potential for atoms

The optimized effective potential equations for atoms have been solved by parameterizing the potential. The expansion is tailored to fulfill the known asymptotic behavior of the effective potential at both short and long distances. Both single configuration and multi configuration trial wave functions are implemented. Applications to several atomic systems are presented improving previous works. The results here obtained are very close to those calculated in either the Hartree-Fock and the multi configurational Hartree-Fock framework.Comment: 8 pages, 3 figure

Ab initio Green's function formalism for band structures

Using the Green's function formalism, an ab initio theory for band structures of crystals is derived starting from the Hartree-Fock approximation. It is based on the algebraic diagrammatic construction scheme for the self-energy which is formulated for crystal orbitals (CO-ADC). In this approach, the poles of the Green's function are determined by solving a suitable Hermitian eigenvalue problem. The method is not only applicable to the outer valence and conduction bands, it is also stable for inner valence bands where strong electron correlations are effective. The key to the proposed scheme is to evaluate the self-energy in terms of Wannier orbitals before transforming it to a crystal momentum representation. Exploiting the fact that electron correlations are mainly local, one can truncate the lattice summations by an appropriate configuration selection scheme. This yields a flat configuration space; i.e., its size scales only linearly with the number of atoms per unit cell for large systems and, under certain conditions, the computational effort to determine band structures also scales linearly. As a first application of the new formalism, a lithium fluoride crystal has been chosen. A minimal basis set description is studied, and a satisfactory agreement with previous theoretical and experimental results for the fundamental band gap and the width of the F 2p valence band complex is obtained.Comment: 20 pages, 3 figures, 1 table, RevTeX4, new section on lithium fluorid

Density-functional Study of Small Molecules within the Krieger-Li-Iafrate Approximation

We report density-functional studies of several small molecules ($H_{2}, N_{2}, CO, H_{2}O$, and $CH_{4}$) within the Krieger-Li-Iafrate (KLI) approximation to the exact Kohn-Sham local exchange potential, using a three-dimensional real-space finite-difference pseudopotential method. It is found that exchange-only KLI leads to markedly improved eigenvalue spectra compared to those obtained within the standard local-density approximation (LDA), the generalized gradient approximation (GGA), and the Hartree-Fock (HF) method. For structural properties, exchange-only KLI results are close to the corresponding HF values. We find that the addition of LDA or GGA correlation energy functionals to the KLI exact exchange energy functional does not lead to systematic improvements.Comment: 16 pages including 1 fugure, to be published in Phys. Rev. A Nov. 1 '9