Lehtovaara, Lauri; Havu, Ville; Puska, Martti
2011-10-21
We present an all-electron method for time-dependent density functional theory which employs hierarchical nonuniform finite-element bases and the time-propagation approach. The method is capable of treating linear and nonlinear response of valence and core electrons to an external field. We also introduce (i) a preconditioner for the propagation equation, (ii) a stable way to implement absorbing boundary conditions, and (iii) a new kind of absorbing boundary condition inspired by perfectly matched layers. PMID:22029294
All-electron Kohn–Sham density functional theory on hierarchic finite element spaces
Schauer, Volker; Linder, Christian
2013-10-01
In this work, a real space formulation of the Kohn–Sham equations is developed, making use of the hierarchy of finite element spaces from different polynomial order. The focus is laid on all-electron calculations, having the highest requirement onto the basis set, which must be able to represent the orthogonal eigenfunctions as well as the electrostatic potential. A careful numerical analysis is performed, which points out the numerical intricacies originating from the singularity of the nuclei and the necessity for approximations in the numerical setting, with the ambition to enable solutions within a predefined accuracy. In this context the influence of counter-charges in the Poisson equation, the requirement of a finite domain size, numerical quadratures and the mesh refinement are examined as well as the representation of the electrostatic potential in a high order finite element space. The performance and accuracy of the method is demonstrated in computations on noble gases. In addition the finite element basis proves its flexibility in the calculation of the bond-length as well as the dipole moment of the carbon monoxide molecule.
Kuwahara, Riichi; Tadokoro, Yoichi; Ohno, Kaoru
2014-08-28
In this paper, we calculate kinetic and potential energy contributions to the electronic ground-state total energy of several isolated atoms (He, Be, Ne, Mg, Ar, and Ca) by using the local density approximation (LDA) in density functional theory, the Hartree-Fock approximation (HFA), and the self-consistent GW approximation (GWA). To this end, we have implemented self-consistent HFA and GWA routines in our all-electron mixed basis code, TOMBO. We confirm that virial theorem is fairly well satisfied in all of these approximations, although the resulting eigenvalue of the highest occupied molecular orbital level, i.e., the negative of the ionization potential, is in excellent agreement only in the case of the GWA. We find that the wave function of the lowest unoccupied molecular orbital level of noble gas atoms is a resonating virtual bound state, and that of the GWA spreads wider than that of the LDA and thinner than that of the HFA. PMID:25173006
NASA Astrophysics Data System (ADS)
Rivelino, Roberto; Malaspina, Thaciana; Fileti, Eudes E.
2009-01-01
We have investigated the stability, electronic properties, Rayleigh (elastic), and Raman (inelastic) depolarization ratios, infrared and Raman absorption vibrational spectra of fullerenols [C60(OH)n] with different degrees of hydroxylation by using all-electron density-functional-theory (DFT) methods. Stable arrangements of these molecules were found by means of full geometry optimizations using Becke’s three-parameter exchange functional with the Lee, Yang, and Parr correlation functional. This DFT level has been combined with the 6-31G(d,p) Gaussian-type basis set, as a compromise between accuracy and capability to treat highly hydroxylated fullerenes, e.g., C60(OH)36 . Thus, the molecular properties of fullerenols were systematically analyzed for structures with n=1 , 2, 3, 4, 8, 10, 16, 18, 24, 32, and 36. From the electronic structure analysis of these molecules, we have evidenced an important effect related to the weak chemical reactivity of a possible C60(OH)24 isomer. To investigate Raman scattering and the vibrational spectra of the different fullerenols, frequency calculations are carried out within the harmonic approximation. In this case a systematic study is only performed for n=1-4 , 8, 10, 16, 18, and 24. Our results give good agreements with the expected changes in the spectral absorptions due to the hydroxylation of fullerenes.
Gulans, Andris; Kontur, Stefan; Meisenbichler, Christian; Nabok, Dmitrii; Pavone, Pasquale; Rigamonti, Santiago; Sagmeister, Stephan; Werner, Ute; Draxl, Claudia
2014-09-10
Linearized augmented planewave methods are known as the most precise numerical schemes for solving the Kohn-Sham equations of density-functional theory (DFT). In this review, we describe how this method is realized in the all-electron full-potential computer package, exciting. We emphasize the variety of different related basis sets, subsumed as (linearized) augmented planewave plus local orbital methods, discussing their pros and cons and we show that extremely high accuracy (microhartrees) can be achieved if the basis is chosen carefully. As the name of the code suggests, exciting is not restricted to ground-state calculations, but has a major focus on excited-state properties. It includes time-dependent DFT in the linear-response regime with various static and dynamical exchange-correlation kernels. These are preferably used to compute optical and electron-loss spectra for metals, molecules and semiconductors with weak electron-hole interactions. exciting makes use of many-body perturbation theory for charged and neutral excitations. To obtain the quasi-particle band structure, the GW approach is implemented in the single-shot approximation, known as G(0)W(0). Optical absorption spectra for valence and core excitations are handled by the solution of the Bethe-Salpeter equation, which allows for the description of strongly bound excitons. Besides these aspects concerning methodology, we demonstrate the broad range of possible applications by prototypical examples, comprising elastic properties, phonons, thermal-expansion coefficients, dielectric tensors and loss functions, magneto-optical Kerr effect, core-level spectra and more. PMID:25135665
Mizutani, U; Inukai, M; Sato, H; Zijlstra, E S; Lin, Q
2014-05-16
There are three key electronic parameters in elucidating the physics behind the Hume–Rothery electron concentration rule: the square of the Fermi diameter (2kF)2, the square of the critical reciprocal lattice vector and the electron concentration parameter or the number of itinerant electrons per atom e/a. We have reliably determined these three parameters for 10 Rhombic Triacontahedron-type 2/1–2/1–2/1 (N = 680) and 1/1–1/1–1/1 (N = 160–162) approximants by making full use of the full-potential linearized augmented plane wave-Fourier band calculations based on all-electron density-functional theory. We revealed that the 2/1–2/1–2/1 approximants Al13Mg27Zn45 and Na27Au27Ga31 belong to two different sub-groups classified in terms of equal to 126 and 109 and could explain why they take different e/a values of 2.13 and 1.76, respectively. Among eight 1/1–1/1–1/1 approximants Al3Mg4Zn3, Al9Mg8Ag3, Al21Li13Cu6, Ga21Li13Cu6, Na26Au24Ga30, Na26Au37Ge18, Na26Au37Sn18 and Na26Cd40Pb6, the first two, the second two and the last four compounds were classified into three sub-groups with = 50, 46 and 42; and were claimed to obey the e/a = 2.30, 2.10–2.15 and 1.70–1.80 rules, respectively.
Mitin, Alexander V; van Wüllen, Christoph
2006-02-14
A two-component quasirelativistic Hamiltonian based on spin-dependent effective core potentials is used to calculate ionization energies and electron affinities of the heavy halogen atom bromine through the superheavy element 117 (eka-astatine) as well as spectroscopic constants of the homonuclear dimers of these atoms. We describe a two-component Hartree-Fock and density-functional program that treats spin-orbit coupling self-consistently within the orbital optimization procedure. A comparison with results from high-order Douglas-Kroll calculations--for the superheavy systems also with zeroth-order regular approximation and four-component Dirac results--demonstrates the validity of the pseudopotential approximation. The density-functional (but not the Hartree-Fock) results show very satisfactory agreement with theoretical coupled cluster as well as experimental data where available, such that the theoretical results can serve as an estimate for the hitherto unknown properties of astatine, element 117, and their dimers. PMID:16483205
Ching, W. Y.; Aryal, Sitram; Rulis, Paul; Schnick, Wolfgang
2011-04-15
Using density-functional-theory-based ab initio methods, the electronic structure and physical properties of the newly synthesized nitride BeP{sub 2}N{sub 4} with a phenakite-type structure and the predicted high-pressure spinel phase of BeP{sub 2}N{sub 4} are studied in detail. It is shown that both polymorphs are wide band-gap semiconductors with relatively small electron effective masses at the conduction-band minima. The spinel-type phase is more covalently bonded due to the increased number of P-N bonds for P at the octahedral sites. Calculations of mechanical properties indicate that the spinel-type polymorph is a promising superhard material with notably large bulk, shear, and Young's moduli. Also calculated are the Be K, P K, P L{sub 3}, and N K edges of the electron energy-loss near-edge structure for both phases. They show marked differences because of the different local environments of the atoms in the two crystalline polymorphs. These differences will be very useful for the experimental identification of the products of high-pressure syntheses targeting the predicted spinel-type phase of BeP{sub 2}N{sub 4}.
NASA Astrophysics Data System (ADS)
Betzinger, Markus; Friedrich, Christoph; Görling, Andreas; Blügel, Stefan
2015-12-01
We present a methodology to calculate frequency and momentum dependent all-electron response functions determined within Kohn-Sham density functional theory. It overcomes the main obstacle in calculating response functions in practice, which is the slow convergence with respect to the number of unoccupied states and the basis-set size. In this approach, the usual sum-over-states expression of perturbation theory is complemented by the response of the orbital basis functions, explicitly constructed by radial integrations of frequency-dependent Sternheimer equations. To an essential extent an infinite number of unoccupied states are included in this way. Furthermore, the response of the core electrons is treated virtually exactly, which is out of reach otherwise. The method is an extension of the recently introduced incomplete-basis-set correction (IBC) [Betzinger et al., Phys. Rev. B 85, 245124 (2012), 10.1103/PhysRevB.85.245124; Phys. Rev. B 88, 075130 (2013), 10.1103/PhysRevB.88.075130] to the frequency and momentum domain. We have implemented the generalized IBC within the all-electron full-potential linearized augmented-plane-wave method and demonstrate for rocksalt BaO the improved convergence of the dynamical Kohn-Sham polarizability. We apply this technique to compute (a) quasiparticle energies employing the COHSEX approximation for the self-energy of many-body perturbation theory and (b) all-electron RPA correlation energies. It is shown that the favorable convergence of the polarizability is passed over to the COHSEX and RPA calculation.
NASA Astrophysics Data System (ADS)
Betzinger, Markus; Friedrich, Christoph; Blügel, Stefan
2013-08-01
In a previous publication [Betzinger, Friedrich, Görling, and Blügel, Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.85.245124 85, 245124 (2012)] we presented a technique to compute accurate all-electron response functions, e.g., the density response function, within the full-potential linearized augmented-plane-wave (FLAPW) method. Response contributions that are not captured (completely) within the finite Hilbert space spanned by the LAPW basis are taken into account by an incomplete-basis-set correction (IBC). The latter is based on a formal response of the basis functions themselves, which is derived by exploiting their dependence on the effective potential. Its construction requires the solution of radial differential equations, having the form of Sternheimer equations, by numerical integration. The approach includes a formally exact treatment of the response contribution from the core states. While we restricted the formalism to spherical perturbations in the previous work, we here generalize the formalism to nonspherical perturbations. The improvements are demonstrated with exact-exchange optimized-effective-potential (EXX-OEP) calculations of antiferromagnetic NiO. It is shown that with the generalized IBC a basis-set convergence is realized that is as fast as in density-functional theory calculations using standard local or semilocal functionals. The EXX-OEP band gap, magnetic moment, and spectral function of NiO are in substantially better agreement with experiment than results obtained from calculations with local and semilocal functionals.
Hybrid functionals within the all-electron FLAPW method: Implementation and applications of PBE0
NASA Astrophysics Data System (ADS)
Betzinger, Markus; Friedrich, Christoph; Blügel, Stefan
2010-05-01
We present an efficient implementation of the Perdew-Burke-Ernzerhof hybrid functional PBE0 within the full-potential linearized augmented-plane-wave (FLAPW) method. The Hartree-Fock exchange term, which is a central ingredient of hybrid functionals, gives rise to a computationally expensive nonlocal potential in the one-particle Schrödinger equation. The matrix elements of this exchange potential are calculated with the help of an auxiliary basis that is constructed from products of FLAPW basis functions. By representing the Coulomb interaction in this basis the nonlocal exchange term becomes a Brillouin-zone sum over vector-matrix-vector products. The Coulomb matrix is calculated only once at the beginning of a self-consistent-field cycle. We show that it can be made sparse by a suitable unitary transformation of the auxiliary basis, which accelerates the computation of the vector-matrix-vector products considerably. Additionally, we exploit spatial and time-reversal symmetry to identify the nonvanishing exchange matrix elements in advance and to restrict the k summations for the nonlocal potential to an irreducible set of k points. Favorable convergence of the self-consistent-field cycle is achieved by a nested density-only and density-matrix iteration scheme. We discuss the convergence with respect to the parameters of our numerical scheme and show results for a variety of semiconductors and insulators, including the oxides ZnO, EuO, Al2O3 , and SrTiO3 , where the PBE0 hybrid functional improves the band gaps and the description of localized states in comparison with the PBE functional. Furthermore, we find that in contrast to conventional local exchange-correlation functionals ferromagnetic EuO is correctly predicted to be a semiconductor.
NASA Astrophysics Data System (ADS)
Matveev, Oleg; Shvaika, Andrij; Devereaux, Thomas; Freericks, James
The charge-density-wave phase of the Falicov-Kimball model displays a number of anomalous behavior including the appearance of subgap density of states as the temperature increases. These subgap states should have a significant impact on transport properties, particularly the nonlinear response of the system to a large dc electric field. Using the Kadanoff-Baym-Keldysh formalism, we employ nonequilibrium dynamical mean-field theory to exactly solve for this nonlinear response. We examine both the current and the order parameter of the conduction electrons as the ordered system is driven by a dc electric field. Institute for Condensed Matter Physics of the National Academy of Sciences of Ukraine, Lviv, Ukraine.
NASA Astrophysics Data System (ADS)
Betzinger, Markus; Friedrich, Christoph; Görling, Andreas; Blügel, Stefan
2012-06-01
The optimized-effective-potential method is a special technique to construct local Kohn-Sham potentials from general orbital-dependent energy functionals. In a recent publication [M. Betzinger, C. Friedrich, S. Blügel, A. Görling, Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.83.045105 83, 045105 (2011)] we showed that uneconomically large basis sets were required to obtain a smooth local potential without spurious oscillations within the full-potential linearized augmented-plane-wave method. This could be attributed to the slow convergence behavior of the density response function. In this paper, we derive an incomplete-basis-set correction for the response, which consists of two terms: (1) a correction that is formally similar to the Pulay correction in atomic-force calculations and (2) a numerically more important basis response term originating from the potential dependence of the basis functions. The basis response term is constructed from the solutions of radial Sternheimer equations in the muffin-tin spheres. With these corrections the local potential converges at much smaller basis sets, at much fewer states, and its construction becomes numerically very stable. We analyze the improvements for rock-salt ScN and report results for BN, AlN, and GaN, as well as the perovskites CaTiO3, SrTiO3, and BaTiO3. The incomplete-basis-set correction can be applied to other electronic-structure methods with potential-dependent basis sets and opens the perspective to investigate a broad spectrum of problems in theoretical solid-state physics that involve response functions.
NASA Astrophysics Data System (ADS)
Levchenko, Sergey V.; Ren, Xinguo; Wieferink, Jürgen; Johanni, Rainer; Rinke, Patrick; Blum, Volker; Scheffler, Matthias
2015-07-01
We describe a framework to evaluate the Hartree-Fock exchange operator for periodic electronic-structure calculations based on general, localized atom-centered basis functions. The functionality is demonstrated by hybrid-functional calculations of properties for several semiconductors. In our implementation of the Fock operator, the Coulomb potential is treated either in reciprocal space or in real space, where the sparsity of the density matrix can be exploited for computational efficiency. Computational aspects, such as the rigorous avoidance of on-the-fly disk storage, and a load-balanced parallel implementation, are also discussed. We demonstrate linear scaling of our implementation with system size by calculating the electronic structure of a bulk semiconductor (GaAs) with up to 1,024 atoms per unit cell without compromising the accuracy.
Gedanken densities and exact constraints in density functional theory
Perdew, John P.; Ruzsinszky, Adrienn; Sun, Jianwei; Burke, Kieron
2014-05-14
Approximations to the exact density functional for the exchange-correlation energy of a many-electron ground state can be constructed by satisfying constraints that are universal, i.e., valid for all electron densities. Gedanken densities are designed for the purpose of this construction, but need not be realistic. The uniform electron gas is an old gedanken density. Here, we propose a spherical two-electron gedanken density in which the dimensionless density gradient can be an arbitrary positive constant wherever the density is non-zero. The Lieb-Oxford lower bound on the exchange energy can be satisfied within a generalized gradient approximation (GGA) by bounding its enhancement factor or simplest GGA exchange-energy density. This enhancement-factor bound is well known to be sufficient, but our gedanken density shows that it is also necessary. The conventional exact exchange-energy density satisfies no such local bound, but energy densities are not unique, and the simplest GGA exchange-energy density is not an approximation to it. We further derive a strongly and optimally tightened bound on the exchange enhancement factor of a two-electron density, which is satisfied by the local density approximation but is violated by all published GGA's or meta-GGA’s. Finally, some consequences of the non-uniform density-scaling behavior for the asymptotics of the exchange enhancement factor of a GGA or meta-GGA are given.
Sharkey, Keeper L.; Pavanello, Michele; Bubin, Sergiy; Adamowicz, Ludwik
2009-12-15
A new algorithm for calculating the Hamiltonian matrix elements with all-electron explicitly correlated Gaussian functions for quantum-mechanical calculations of atoms with two p electrons or a single d electron have been derived and implemented. The Hamiltonian used in the approach was obtained by rigorously separating the center-of-mass motion and it explicitly depends on the finite mass of the nucleus. The approach was employed to perform test calculations on the isotopes of the carbon atom in their ground electronic states and to determine the finite-nuclear-mass corrections for these states.
Sharkey, Keeper L; Kirnosov, Nikita; Adamowicz, Ludwik
2013-03-14
A new algorithm for quantum-mechanical nonrelativistic calculation of the Hamiltonian matrix elements with all-electron explicitly correlated Gaussian functions for atoms with an arbitrary number of s electrons and with three p electrons, or one p electron and one d electron, or one f electron is developed and implemented. In particular the implementation concerns atomic states with L = 3 and M = 0. The Hamiltonian used in the approach is obtained by rigorously separating the center-of-mass motion from the laboratory-frame all particle Hamiltonian, and thus it explicitly depends on the finite mass of the nucleus. The approach is employed to perform test calculations on the lowest (2)F state of the two main isotopes of the lithium atom, (7)Li and (6)Li. PMID:23514465
Partition density functional theory
NASA Astrophysics Data System (ADS)
Nafziger, Jonathan
Partition density functional theory (PDFT) is a method for dividing a molecular electronic structure calculation into fragment calculations. The molecular density and energy corresponding to Kohn Sham density-functional theory (KS-DFT) may be exactly recovered from these fragments. Each fragment acts as an isolated system except for the influence of a global one-body 'partition' potential which deforms the fragment densities. In this work, the developments of PDFT are put into the context of other fragment-based density functional methods. We developed three numerical implementations of PDFT: One within the NWChem computational chemistry package using basis sets, and the other two developed from scratch using real-space grids. It is shown that all three of these programs can exactly reproduce a KS-DFT calculation via fragment calculations. The first of our in-house codes handles non-interacting electrons in arbitrary one-dimensional potentials with any number of fragments. This code is used to explore how the exact partition potential changes for different partitionings of the same system and also to study features which determine which systems yield non-integer PDFT occupations and which systems are locked into integer PDFT occupations. The second in-house code, CADMium, performs real-space calculations of diatomic molecules. Features of the exact partition potential are studied for a variety of cases and an analytical formula determining singularities in the partition potential is derived. We introduce an approximation for the non-additive kinetic energy and show how this quantity can be computed exactly. Finally a PDFT functional is developed to address the issues of static correlation and delocalization errors in approximations within DFT. The functional is applied to the dissociation of H2 + and H2.
]: a density functional theory investigation
NASA Astrophysics Data System (ADS)
Ulian, Gianfranco; Tosoni, Sergio; Valdrè, Giovanni
2014-09-01
In this work, we modelled the structure, the compressional behaviour and the physical properties of talc over a wide range of pressure using a quantum mechanical approach based on periodic boundary conditions. We adopted the density functional theory using the B3LYP-D* functional, which includes a correction for the dispersive forces and all-electron Gaussian-type orbitals basis sets. An atomic level description of the athermal pressure-induced structural modification of talc is provided. From the compression results, we obtained the athermal ( T = 0 K) bulk modulus ( K T0), its first derivative ( K') and the athermal volume at zero pressure ( V 0) by a third-order Birch-Murnaghan equation with parameters K T0 = 56.25 GPa, K' = 5.66 and V 0 = 450.34 Å3. The mechanical behaviour is highly anisotropic, as observed by the axial compressibility. The presented data are in very good agreement with recent experimental results obtained by single-crystal neutron and X-ray diffraction experiments.
Evarestov, R A; Losev, M V
2009-12-01
For the first time the convergence of the phonon frequencies and dispersion curves in terms of the supercell size is studied in ab initio frozen phonon calculations on LiF crystal. Helmann-Feynman forces over atomic displacements are found in all-electron calculations with the localized atomic functions (LCAO) basis using CRYSTAL06 program. The Parlinski-Li-Kawazoe method and FROPHO program are used to calculate the dynamical matrix and phonon frequencies of the supercells. For fcc lattice, it is demonstrated that use of the full supercell space group (including the supercell inner translations) enables to reduce essentially the number of the displacements under consideration. For Hartree-Fock (HF), PBE and hybrid PBE0, B3LYP, and B3PW exchange-correlation functionals the atomic basis set optimization is performed. The supercells up to 216 atoms (3 x 3 x 3 conventional unit cells) are considered. The phonon frequencies using the supercells of different size and shape are compared. For the commensurate with supercell k-points the best agreement of the theoretical results with the experimental data is found for B3PW exchange-correlation functional calculations with the optimized basis set. The phonon frequencies at the most non-commensurate k-points converged for the supercell consisting of 4 x 4 x 4 primitive cells and ensures the accuracy 1-2% in the thermodynamic properties calculated (the Helmholtz free energy, entropy, and heat capacity at the room temperature). PMID:19382176
Density-dependent covariant energy density functionals
Lalazissis, G. A.
2012-10-20
Relativistic nuclear energy density functionals are applied to the description of a variety of nuclear structure phenomena at and away fromstability line. Isoscalar monopole, isovector dipole and isoscalar quadrupole giant resonances are calculated using fully self-consistent relativistic quasiparticle randomphase approximation, based on the relativistic Hartree-Bogoliubovmodel. The impact of pairing correlations on the fission barriers in heavy and superheavy nuclei is examined. The role of pion in constructing desnity functionals is also investigated.
Phenomenological Relativistic Energy Density Functionals
Lalazissis, G. A.; Kartzikos, S.; Niksic, T.; Paar, N.; Vretenar, D.; Ring, P.
2009-08-26
The framework of relativistic nuclear energy density functionals is applied to the description of a variety of nuclear structure phenomena, not only in spherical and deformed nuclei along the valley of beta-stability, but also in exotic systems with extreme isospin values and close to the particle drip-lines. Dynamical aspects of exotic nuclear structure is explored using the fully consistent quasiparticle random-phase approximation based on the relativistic Hartree-Bogoliubov model. Recent applications of energy density functionals with explicit density dependence of the meson-nucleon couplings are presented.
Density Functionals of Chemical Bonding
Putz, Mihai V.
2008-01-01
The behavior of electrons in general many-electronic systems throughout the density functionals of energy is reviewed. The basic physico-chemical concepts of density functional theory are employed to highlight the energy role in chemical structure while its extended influence in electronic localization function helps in chemical bonding understanding. In this context the energy functionals accompanied by electronic localization functions may provide a comprehensive description of the global-local levels electronic structures in general and of chemical bonds in special. Becke-Edgecombe and author’s Markovian electronic localization functions are discussed at atomic, molecular and solid state levels. Then, the analytical survey of the main workable kinetic, exchange, and correlation density functionals within local and gradient density approximations is undertaken. The hierarchy of various energy functionals is formulated by employing both the parabolic and statistical correlation degree of them with the electronegativity and chemical hardness indices by means of quantitative structure-property relationship (QSPR) analysis for basic atomic and molecular systems. PMID:19325846
Semiclassical origins of density functionals
NASA Astrophysics Data System (ADS)
Burke, Kieron
By careful numerical analysis of non-relativistic atomic correlation energies, we show that (a) the local density approximation becomes relatively exact for the correlation energy as the atomic number approaches infinity, (b) we find the leading correction, which is about 38.5 milliHartrees per atom, (c) show how this correction dominates for larger atoms and (d) how to construct a generalized gradient approximation that respects this limit (See KB, A. Cancio, T. Gould, S. Pittalis, arXiv:1409.4834). The relevance to density functional calculations will also be explained. Support provided by NSF CHE-1464795.
NASA Astrophysics Data System (ADS)
Sharkey, Keeper L.; Bubin, Sergiy; Adamowicz, Ludwik
2014-11-01
Accurate variational nonrelativistic quantum-mechanical calculations are performed for the five lowest 1D and four lowest 3D states of the 9Be isotope of the beryllium atom. All-electron explicitly correlated Gaussian (ECG) functions are used in the calculations and their nonlinear parameters are optimized with the aid of the analytical energy gradient determined with respect to these parameters. The effect of the finite nuclear mass is directly included in the Hamiltonian used in the calculations. The singlet-triplet energy gaps between the corresponding 1D and 3D states, are reported.
Density functionals from deep learning
NASA Astrophysics Data System (ADS)
McMahon, Jeffrey
Density-functional theory is a formally exact description of a many-body quantum system in terms of its density; in practice, however, approximations to the universal density functional (DF) are necessary. Machine learning has recently been proposed as a novel approach to discover such a DF (or components of it). Conventional machine learning algorithms, however, are limited in their ability to process data in their raw form, leading to invariance and/or sensitivity issues. In this presentation, an alternative approach based on deep learning will be demonstrated. Deep learning allows computational models that are capable of discovering intricate structure in large and/or high-dimensional data sets with multiple levels of abstraction, and do not suffer from the aforementioned issues. Results from the application of this approach to the prediction of the kinetic-energy DF of noninteracting electrons will be presented. Using theoretical results from computer science, a connection between the underlying model and the theorems of Hohenberg and Kohn will also be suggested.
Periodic Density Functional Theory Solver using Multiresolution Analysis with MADNESS
NASA Astrophysics Data System (ADS)
Harrison, Robert; Thornton, William
2011-03-01
We describe the first implementation of the all-electron Kohn-Sham density functional periodic solver (DFT) using multi-wavelets and fast integral equations using MADNESS (multiresolution adaptive numerical environment for scientific simulation; http://code.google.com/p/m-a-d-n-e-s-s). The multiresolution nature of a multi-wavelet basis allows for fast computation with guaranteed precision. By reformulating the Kohn-Sham eigenvalue equation into the Lippmann-Schwinger equation, we can avoid using the derivative operator which allows better control of overall precision for the all-electron problem. Other highlights include the development of periodic integral operators with low-rank separation, an adaptable model potential for nuclear potential, and an implementation for Hartree Fock exchange. This work was supported by NSF project OCI-0904972 and made use of resources at the Center for Computational Sciences at Oak Ridge National Laboratory under contract DE-AC05-00OR22725.
Density functional theory: Foundations reviewed
NASA Astrophysics Data System (ADS)
Kryachko, Eugene S.; Ludeña, Eduardo V.
2014-11-01
Guided by the above motto (quotation), we review a broad range of issues lying at the foundations of Density Functional Theory, DFT, a theory which is currently omnipresent in our everyday computational study of atoms and molecules, solids and nano-materials, and which lies at the heart of modern many-body computational technologies. The key goal is to demonstrate that there are definitely the ways to improve DFT. We start by considering DFT in the larger context provided by reduced density matrix theory (RDMT) and natural orbital functional theory (NOFT), and examine the implications that N-representability conditions on the second-order reduced density matrix (2-RDM) have not only on RDMT and NOFT but, also, by extension, on the functionals of DFT. This examination is timely in view of the fact that necessary and sufficient N-representability conditions on the 2-RDM have recently been attained. In the second place, we review some problems appearing in the original formulation of the first Hohenberg-Kohn theorem which is still a subject of some controversy. In this vein we recall Lieb's comment on this proof and the extension to this proof given by Pino et al. (2009), and in this context examine the conditions that must be met in order that the one-to-one correspondence between ground-state densities and external potentials remains valid for finite subspaces (namely, the subspaces where all Kohn-Sham solutions are obtained in practical applications). We also consider the issue of whether the Kohn-Sham equations can be derived from basic principles or whether they are postulated. We examine this problem in relation to ab initio DFT. The possibility of postulating arbitrary Kohn-Sham-type equations, where the effective potential is by definition some arbitrary mixture of local and non-local terms, is discussed. We also deal with the issue of whether there exists a universal functional, or whether one should advocate instead the construction of problem
Sharkey, Keeper L; Adamowicz, Ludwik
2014-05-01
An algorithm for quantum-mechanical nonrelativistic variational calculations of L = 0 and M = 0 states of atoms with an arbitrary number of s electrons and with three p electrons have been implemented and tested in the calculations of the ground (4)S state of the nitrogen atom. The spatial part of the wave function is expanded in terms of all-electrons explicitly correlated Gaussian functions with the appropriate pre-exponential Cartesian angular factors for states with the L = 0 and M = 0 symmetry. The algorithm includes formulas for calculating the Hamiltonian and overlap matrix elements, as well as formulas for calculating the analytic energy gradient determined with respect to the Gaussian exponential parameters. The gradient is used in the variational optimization of these parameters. The Hamiltonian used in the approach is obtained by rigorously separating the center-of-mass motion from the laboratory-frame all-particle Hamiltonian, and thus it explicitly depends on the finite mass of the nucleus. With that, the mass effect on the total ground-state energy is determined. PMID:24811630
Unexpected properties of a density functional
Karwowski, J.; Stanke, M.
2005-02-01
An observation on a pathological behavior of an exact density functional derived from either relativistic (Dirac) or nonrelativistic (Levy-Leblond) quantum-mechanical equation is reported. As expected, in the case of a one-electron atom the variational minimum of this functional is equal to the exact ground-state energy. However, apart from the correct density, this minimum is reached also by an infinite set of densities which do not correspond to the exact wave function. This paradoxical property of the functional is related to the multicomponent structure of both Dirac and Levy-Leblond wave functions. In particular, imposing the correct boundary conditions upon the trial densities removes only a part of the fake solutions. The results of this study demonstrate that in density-functional theories derived from models based on multicomponent wave functions, one should not expect any simple relation between the accuracy of the energy and the correctness of the corresponding density.
Orbital-free density functional theory implementation with the projector augmented-wave method
NASA Astrophysics Data System (ADS)
Lehtomäki, Jouko; Makkonen, Ilja; Caro, Miguel A.; Harju, Ari; Lopez-Acevedo, Olga
2014-12-01
We present a computational scheme for orbital-free density functional theory (OFDFT) that simultaneously provides access to all-electron values and preserves the OFDFT linear scaling as a function of the system size. Using the projector augmented-wave method (PAW) in combination with real-space methods, we overcome some obstacles faced by other available implementation schemes. Specifically, the advantages of using the PAW method are twofold. First, PAW reproduces all-electron values offering freedom in adjusting the convergence parameters and the atomic setups allow tuning the numerical accuracy per element. Second, PAW can provide a solution to some of the convergence problems exhibited in other OFDFT implementations based on Kohn-Sham (KS) codes. Using PAW and real-space methods, our orbital-free results agree with the reference all-electron values with a mean absolute error of 10 meV and the number of iterations required by the self-consistent cycle is comparable to the KS method. The comparison of all-electron and pseudopotential bulk modulus and lattice constant reveal an enormous difference, demonstrating that in order to assess the performance of OFDFT functionals it is necessary to use implementations that obtain all-electron values. The proposed combination of methods is the most promising route currently available. We finally show that a parametrized kinetic energy functional can give lattice constants and bulk moduli comparable in accuracy to those obtained by the KS PBE method, exemplified with the case of diamond.
Orbital-free density functional theory implementation with the projector augmented-wave method
Lehtomäki, Jouko; Makkonen, Ilja; Harju, Ari; Lopez-Acevedo, Olga; Caro, Miguel A.
2014-12-21
We present a computational scheme for orbital-free density functional theory (OFDFT) that simultaneously provides access to all-electron values and preserves the OFDFT linear scaling as a function of the system size. Using the projector augmented-wave method (PAW) in combination with real-space methods, we overcome some obstacles faced by other available implementation schemes. Specifically, the advantages of using the PAW method are twofold. First, PAW reproduces all-electron values offering freedom in adjusting the convergence parameters and the atomic setups allow tuning the numerical accuracy per element. Second, PAW can provide a solution to some of the convergence problems exhibited in other OFDFT implementations based on Kohn-Sham (KS) codes. Using PAW and real-space methods, our orbital-free results agree with the reference all-electron values with a mean absolute error of 10 meV and the number of iterations required by the self-consistent cycle is comparable to the KS method. The comparison of all-electron and pseudopotential bulk modulus and lattice constant reveal an enormous difference, demonstrating that in order to assess the performance of OFDFT functionals it is necessary to use implementations that obtain all-electron values. The proposed combination of methods is the most promising route currently available. We finally show that a parametrized kinetic energy functional can give lattice constants and bulk moduli comparable in accuracy to those obtained by the KS PBE method, exemplified with the case of diamond.
A Safari Through Density Functional Theory
NASA Astrophysics Data System (ADS)
Dreizler, Reiner M.; Lüdde, Cora S.
Density functional theory is widely used to treat quantum many body problems in many areas of physics and related fields. A brief survey of this method covering foundations, functionals and applications is presented here.
Magnetic fields and density functional theory
Salsbury Jr., Freddie
1999-02-01
A major focus of this dissertation is the development of functionals for the magnetic susceptibility and the chemical shielding within the context of magnetic field density functional theory (BDFT). These functionals depend on the electron density in the absence of the field, which is unlike any other treatment of these responses. There have been several advances made within this theory. The first of which is the development of local density functionals for chemical shieldings and magnetic susceptibilities. There are the first such functionals ever proposed. These parameters have been studied by constructing functionals for the current density and then using the Biot-Savart equations to obtain the responses. In order to examine the advantages and disadvantages of the local functionals, they were tested numerically on some small molecules.
Density functional theory for carbon dioxide crystal
Chang, Yiwen; Mi, Jianguo Zhong, Chongli
2014-05-28
We present a density functional approach to describe the solid−liquid phase transition, interfacial and crystal structure, and properties of polyatomic CO{sub 2}. Unlike previous phase field crystal model or density functional theory, which are derived from the second order direct correlation function, the present density functional approach is based on the fundamental measure theory for hard-sphere repulsion in solid. More importantly, the contributions of enthalpic interactions due to the dispersive attractions and of entropic interactions arising from the molecular architecture are integrated in the density functional model. Using the theoretical model, the predicted liquid and solid densities of CO{sub 2} at equilibrium triple point are in good agreement with the experimental values. Based on the structure of crystal-liquid interfaces in different planes, the corresponding interfacial tensions are predicted. Their respective accuracies need to be tested.
Accurate density functional thermochemistry for larger molecules.
Raghavachari, K.; Stefanov, B. B.; Curtiss, L. A.; Lucent Tech.
1997-06-20
Density functional methods are combined with isodesmic bond separation reaction energies to yield accurate thermochemistry for larger molecules. Seven different density functionals are assessed for the evaluation of heats of formation, Delta H 0 (298 K), for a test set of 40 molecules composed of H, C, O and N. The use of bond separation energies results in a dramatic improvement in the accuracy of all the density functionals. The B3-LYP functional has the smallest mean absolute deviation from experiment (1.5 kcal mol/f).
Locality of correlation in density functional theory
NASA Astrophysics Data System (ADS)
Burke, Kieron; Cancio, Antonio; Gould, Tim; Pittalis, Stefano
2016-08-01
The Hohenberg-Kohn density functional was long ago shown to reduce to the Thomas-Fermi (TF) approximation in the non-relativistic semiclassical (or large-Z) limit for all matter, i.e., the kinetic energy becomes local. Exchange also becomes local in this limit. Numerical data on the correlation energy of atoms support the conjecture that this is also true for correlation, but much less relevant to atoms. We illustrate how expansions around a large particle number are equivalent to local density approximations and their strong relevance to density functional approximations. Analyzing highly accurate atomic correlation energies, we show that EC → -AC ZlnZ + BCZ as Z → ∞, where Z is the atomic number, AC is known, and we estimate BC to be about 37 mhartree. The local density approximation yields AC exactly, but a very incorrect value for BC, showing that the local approximation is less relevant for the correlation alone. This limit is a benchmark for the non-empirical construction of density functional approximations. We conjecture that, beyond atoms, the leading correction to the local density approximation in the large-Z limit generally takes this form, but with BC a functional of the TF density for the system. The implications for the construction of approximate density functionals are discussed.
Locality of correlation in density functional theory.
Burke, Kieron; Cancio, Antonio; Gould, Tim; Pittalis, Stefano
2016-08-01
The Hohenberg-Kohn density functional was long ago shown to reduce to the Thomas-Fermi (TF) approximation in the non-relativistic semiclassical (or large-Z) limit for all matter, i.e., the kinetic energy becomes local. Exchange also becomes local in this limit. Numerical data on the correlation energy of atoms support the conjecture that this is also true for correlation, but much less relevant to atoms. We illustrate how expansions around a large particle number are equivalent to local density approximations and their strong relevance to density functional approximations. Analyzing highly accurate atomic correlation energies, we show that EC → -AC ZlnZ + BCZ as Z → ∞, where Z is the atomic number, AC is known, and we estimate BC to be about 37 mhartree. The local density approximation yields AC exactly, but a very incorrect value for BC, showing that the local approximation is less relevant for the correlation alone. This limit is a benchmark for the non-empirical construction of density functional approximations. We conjecture that, beyond atoms, the leading correction to the local density approximation in the large-Z limit generally takes this form, but with BC a functional of the TF density for the system. The implications for the construction of approximate density functionals are discussed. PMID:27497544
Particle conservation in dynamical density functional theory
NASA Astrophysics Data System (ADS)
de las Heras, Daniel; Brader, Joseph M.; Fortini, Andrea; Schmidt, Matthias
2016-06-01
We present the exact adiabatic theory for the dynamics of the inhomogeneous density distribution of a classical fluid. Erroneous particle number fluctuations of dynamical density functional theory are absent, both for canonical and grand canonical initial conditions. We obtain the canonical free energy functional, which yields the adiabatic interparticle forces of overdamped Brownian motion. Using an exact and one of the most advanced approximate hard core free energy functionals, we obtain excellent agreement with simulations. The theory applies to finite systems in and out of equilibrium.
Particle conservation in dynamical density functional theory.
de Las Heras, Daniel; Brader, Joseph M; Fortini, Andrea; Schmidt, Matthias
2016-06-22
We present the exact adiabatic theory for the dynamics of the inhomogeneous density distribution of a classical fluid. Erroneous particle number fluctuations of dynamical density functional theory are absent, both for canonical and grand canonical initial conditions. We obtain the canonical free energy functional, which yields the adiabatic interparticle forces of overdamped Brownian motion. Using an exact and one of the most advanced approximate hard core free energy functionals, we obtain excellent agreement with simulations. The theory applies to finite systems in and out of equilibrium. PMID:27115673
Nonlocal kinetic-energy-density functionals
Garcia-Gonzalez, P.; Alvarellos, J.E.; Chacon, E. |
1996-04-01
In this paper we present nonlocal kinetic-energy functionals {ital T}[{ital n}] within the average density approximation (ADA) framework, which do not require any extra input when applied to any electron system and recover the exact kinetic energy and the linear response function of a homogeneous system. In contrast with previous ADA functionals, these present good behavior of the long-range tail of the exact weight function. The averaging procedure for the kinetic functional (averaging the Fermi momentum of the electron gas, instead of averaging the electron density) leads to a functional without numerical difficulties in the calculation of extended systems, and it gives excellent results when applied to atoms and jellium surfaces. {copyright} {ital 1996 The American Physical Society.}
Density Functionals with Broad Applicability in Chemistry
Zhao, Yan; Truhlar, Donald G.
2008-02-01
The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Although density functional theory is widely used in the computational chemistry community, the most popular density functional, B3LYP, has some serious shortcomings: (i) it is better for main-group chemistry than for transition metals; (ii) it systematically underestimates reaction barrier heights; (iii) it is inaccurate for interactions dominated by mediumrange correlation energy, such as van der Waals attraction, aromatic-aromatic stacking, and alkane isomerization energies. We have developed a variety of databases for testing and designing new density functionals. We used these data to design new density functionals, called M06-class (and, earlier, M05-class) functionals, for which we enforced some fundamental exact constraints such as the uniform-electron-gas limit and the absence of self-correlation energy. Our M06-class functionals depend on spin-up and spin-down electron densities (i.e., spin densities), spin density gradients, spin kinetic energy densities, and, for nonlocal (also called hybrid) functionals, Hartree-Fock exchange. We have developed four new functionals that overcome the above-mentioned difficulties: (a) M06, a hybrid meta functional, is a functional with good accuracy “across-theboard” for transition metals, main group thermochemistry, medium-range correlation energy, and barrier heights; (b) M06- 2X, another hybrid meta functional, is not good for transition metals but has excellent performance for main group chemistry, predicts accurate valence and Rydberg electronic excitation energies, and is an excellent functional for aromatic-aromatic stacking interactions; (c) M06-L is not as accurate as M06 for barrier heights but is the most accurate
Periodic subsystem density-functional theory
Genova, Alessandro; Pavanello, Michele; Ceresoli, Davide
2014-11-07
By partitioning the electron density into subsystem contributions, the Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) has recently emerged as a powerful tool for reducing the computational scaling of Kohn–Sham DFT. To date, however, FDE has been employed to molecular systems only. Periodic systems, such as metals, semiconductors, and other crystalline solids have been outside the applicability of FDE, mostly because of the lack of a periodic FDE implementation. To fill this gap, in this work we aim at extending FDE to treat subsystems of molecular and periodic character. This goal is achieved by a dual approach. On one side, the development of a theoretical framework for periodic subsystem DFT. On the other, the realization of the method into a parallel computer code. We find that periodic FDE is capable of reproducing total electron densities and (to a lesser extent) also interaction energies of molecular systems weakly interacting with metallic surfaces. In the pilot calculations considered, we find that FDE fails in those cases where there is appreciable density overlap between the subsystems. Conversely, we find FDE to be in semiquantitative agreement with Kohn–Sham DFT when the inter-subsystem density overlap is low. We also conclude that to make FDE a suitable method for describing molecular adsorption at surfaces, kinetic energy density functionals that go beyond the GGA level must be employed.
Connection formulas for thermal density functional theory
NASA Astrophysics Data System (ADS)
Pribram-Jones, A.; Burke, K.
2016-05-01
The adiabatic connection formula of ground-state density functional theory relates the correlation energy to a coupling-constant integral over a purely potential contribution, and is widely used to understand and improve approximations. The corresponding formula for thermal density functional theory is cast as an integral over temperatures instead, ranging upward from the system's physical temperature. We also show how to relate different correlation components to each other, either in terms of temperature or coupling-constant integrations. We illustrate our results on the uniform electron gas.
Koopmans' condition for density-functional theory
Dabo, Ismaila; Ferretti, Andrea; Poilvert, Nicolas; Marzari, Nicola; Li, Yanli; Cococcioni, Matteo
2010-09-15
In approximate Kohn-Sham density-functional theory, self-interaction manifests itself as the dependence of the energy of an orbital on its fractional occupation. This unphysical behavior translates into qualitative and quantitative errors that pervade many fundamental aspects of density-functional predictions. Here, we first examine self-interaction in terms of the discrepancy between total and partial electron removal energies, and then highlight the importance of imposing the generalized Koopmans' condition - that identifies orbital energies as opposite total electron removal energies - to resolve this discrepancy. In the process, we derive a correction to approximate functionals that, in the frozen-orbital approximation, eliminates the unphysical occupation dependence of orbital energies up to the third order in the single-particle densities. This non-Koopmans correction brings physical meaning to single-particle energies; when applied to common local or semilocal density functionals it provides results that are in excellent agreement with experimental data - with an accuracy comparable to that of GW many-body perturbation theory - while providing an explicit total energy functional that preserves or improves on the description of established structural properties.
Generalized local-spin-density-functional theory
NASA Astrophysics Data System (ADS)
Guo, Yufei; Whitehead, M. A.
1991-01-01
An alternative density-functional theory, the generalized local-spin-density-functional (G-LSD) theory, is proposed based on the boundary conditions and sum rule of the Fermi-correlation factor in the Hartree-Fock (HF) limit. It avoids the physical restrictions to the boundary conditions and the sum rule used in the generalized exchange local-spin-density-functional (GX-LSD) theory completely, the homogeneous electron-density approximation in the Hartree-Fock-Slater (HFS) theory and in the Gáspár-Kohn-Sham (GKS) theory partly, and the time-consuming step to search for the optimal exchange parameter for each atom or ion in the Xα and Ξa theories. The alternative G-LSD theory generates the GX-LSD, HFS, GKS, Xα, and Ξa theories, when additional approximations or certain Fermi-hole shapes or high electron-density limit in a system are used. Theoretically, the G-LSD theory is more rigorous than the GX-LSD, HFS, GKS, and Ξa theories. Numerically, the statistical total energies for atoms in the G-LSD theory are in excellent agreement with the HF results, when the Gopinathan, Whitehead, and Bogdanovic [Phys. Rev. A 14, 1 (1976)] Fermi-hole parameters are used.
Density-functional expansion methods: Grand challenges
Giese, Timothy J.; York, Darrin M.
2016-01-01
We discuss the source of errors in semiempirical density functional expansion (VE) methods. In particular, we show that VE methods are capable of well-reproducing their standard Kohn-Sham density functional method counterparts, but suffer from large errors upon using one or more of these approximations: the limited size of the atomic orbital basis, the Slater monopole auxiliary basis description of the response density, and the one- and two-body treatment of the core-Hamiltonian matrix elements. In the process of discussing these approximations and highlighting their symptoms, we introduce a new model that supplements the second-order density-functional tight-binding model with a self-consistent charge-dependent chemical potential equalization correction; we review our recently reported method for generalizing the auxiliary basis description of the atomic orbital response density; and we decompose the first-order potential into a summation of additive atomic components and many-body corrections, and from this examination, we provide new insights and preliminary results that motivate and inspire new approximate treatments of the core-Hamiltonian. PMID:27293378
Communication: Embedded fragment stochastic density functional theory
Neuhauser, Daniel; Baer, Roi; Rabani, Eran
2014-07-28
We develop a method in which the electronic densities of small fragments determined by Kohn-Sham density functional theory (DFT) are embedded using stochastic DFT to form the exact density of the full system. The new method preserves the scaling and the simplicity of the stochastic DFT but cures the slow convergence that occurs when weakly coupled subsystems are treated. It overcomes the spurious charge fluctuations that impair the applications of the original stochastic DFT approach. We demonstrate the new approach on a fullerene dimer and on clusters of water molecules and show that the density of states and the total energy can be accurately described with a relatively small number of stochastic orbitals.
Density functional theory studies of etoricoxib
NASA Astrophysics Data System (ADS)
Sachdeva, Ritika; Kaur, Prabhjot; Singh, V. P.; Saini, G. S. S.
2016-05-01
Etoricoxib is a COX-2 selective inhibitor drug with molecular formula C18H15ClN2O2S. It is primarily used for the treatment of arthritis(rheumatoid, psoriatic, osteoarthritis), ankylosing spondylitis, gout and chronic low back pain. Theoretical studies of the molecule including geometry optimization and vibrational frequency calculations were carried out with the help of density functional theory calculations using 6-311++ g (d, p) basis set and B3LYP functional.
Nuclear moments in covariant density functional theory
NASA Astrophysics Data System (ADS)
Meng, J.; Zhao, P. W.; Zhang, S. Q.; Hu, J. N.; Li, J.
2014-05-01
Recent progresses on microscopic and self-consistent description of the nuclear moments in covariant density functional theory based on a point-coupling interaction are briefly reviewed. In particular, the electric quadrupole moments of Cd isotopes and the magnetic moments of Pb isotopes are discussed.
Probability density function learning by unsupervised neurons.
Fiori, S
2001-10-01
In a recent work, we introduced the concept of pseudo-polynomial adaptive activation function neuron (FAN) and presented an unsupervised information-theoretic learning theory for such structure. The learning model is based on entropy optimization and provides a way of learning probability distributions from incomplete data. The aim of the present paper is to illustrate some theoretical features of the FAN neuron, to extend its learning theory to asymmetrical density function approximation, and to provide an analytical and numerical comparison with other known density function estimation methods, with special emphasis to the universal approximation ability. The paper also provides a survey of PDF learning from incomplete data, as well as results of several experiments performed on real-world problems and signals. PMID:11709808
Differentiability of Lieb functional in electronic density functional theory
NASA Astrophysics Data System (ADS)
Lammert, Paul E.
A solid understanding of the Lieb functional FL is important because of its centrality in the foundations of electronic density functional theory. A basic question is whether directional derivatives of FL at an ensemble-V-representable density are given by (minus) the potential. A widely accepted purported proof that FL is Gâteaux differentiable at EV-representable densities would say, ?yes.? But that proof is fallacious, as shown here. FL is not Gâteaux differentiable in the normal sense, nor is it continuous. By means of a constructive approach, however, we are able to show that the derivative of FL at an EV-representable density ?0 in the direction of ?1 is given by the potential if ?0 and ?1 are everywhere strictly greater than zero, and they and the ground state wave function have square integrable derivatives through second order.
Density gradient expansion of correlation functions
NASA Astrophysics Data System (ADS)
van Leeuwen, Robert
2013-04-01
We present a general scheme based on nonlinear response theory to calculate the expansion of correlation functions such as the pair-correlation function or the exchange-correlation hole of an inhomogeneous many-particle system in terms of density derivatives of arbitrary order. We further derive a consistency condition that is necessary for the existence of the gradient expansion. This condition is used to carry out an infinite summation of terms involving response functions up to infinite order from which it follows that the coefficient functions of the gradient expansion can be expressed in terms of the local density profile rather than the background density around which the expansion is carried out. We apply the method to the calculation of the gradient expansion of the one-particle density matrix to second order in the density gradients and recover in an alternative manner the result of Gross and Dreizler [Gross and Dreizler, Z. Phys. AZPAADB0340-219310.1007/BF01413038 302, 103 (1981)], which was derived using the Kirzhnits method. The nonlinear response method is more general and avoids the turning point problem of the Kirzhnits expansion. We further give a description of the exchange hole in momentum space and confirm the wave vector analysis of Langreth and Perdew [Langreth and Perdew, Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.21.5469 21, 5469 (1980)] for this case. This is used to derive that the second-order gradient expansion of the system averaged exchange hole satisfies the hole sum rule and to calculate the gradient coefficient of the exchange energy without the need to regularize divergent integrals.
Density-Functional Theory of Thermal Transport
NASA Astrophysics Data System (ADS)
Eich, F. G.; Principi, A.; di Ventra, M.; Vignale, G.
2014-03-01
We have recently introduced a non-equilibrium density-functional theory of local temperature and associated energy density that is suitable for the study of thermoelectric phenomena from first principles. This theory rests on a local temperature field coupled to the energy-density operator. Here we apply the theory to a simple two-terminal setup, in which the terminals are held at different temperatures. We show that our treatment becomes equivalent to the standard Landauer-Büttiker formulation of thermal transport in the non-interacting limit. We gratefully acknowledge support from DOE under Grant No. DE-FG02-05ER46203 (FGE, AP, GV) and DE-FG02-05ER46204 (MD).
NASA Astrophysics Data System (ADS)
Pribram-Jones, Aurora
Warm dense matter (WDM) is a high energy phase between solids and plasmas, with characteristics of both. It is present in the centers of giant planets, within the earth's core, and on the path to ignition of inertial confinement fusion. The high temperatures and pressures of warm dense matter lead to complications in its simulation, as both classical and quantum effects must be included. One of the most successful simulation methods is density functional theory-molecular dynamics (DFT-MD). Despite great success in a diverse array of applications, DFT-MD remains computationally expensive and it neglects the explicit temperature dependence of electron-electron interactions known to exist within exact DFT. Finite-temperature density functional theory (FT DFT) is an extension of the wildly successful ground-state DFT formalism via thermal ensembles, broadening its quantum mechanical treatment of electrons to include systems at non-zero temperatures. Exact mathematical conditions have been used to predict the behavior of approximations in limiting conditions and to connect FT DFT to the ground-state theory. An introduction to FT DFT is given within the context of ensemble DFT and the larger field of DFT is discussed for context. Ensemble DFT is used to describe ensembles of ground-state and excited systems. Exact conditions in ensemble DFT and the performance of approximations depend on ensemble weights. Using an inversion method, exact Kohn-Sham ensemble potentials are found and compared to approximations. The symmetry eigenstate Hartree-exchange approximation is in good agreement with exact calculations because of its inclusion of an ensemble derivative discontinuity. Since ensemble weights in FT DFT are temperature-dependent Fermi weights, this insight may help develop approximations well-suited to both ground-state and FT DFT. A novel, highly efficient approach to free energy calculations, finite-temperature potential functional theory, is derived, which has the
Jankowski, K; Nowakowski, K; Grabowski, I; Wasilewski, J
2009-04-28
The problem of linking the dynamic electron correlation effects defined in traditional ab initio methods [or wave function theories (WFTs)] with the structure of the individual density functional theory (DFT) exchange and correlation functionals has been analyzed for the Ne atom, for which nondynamic correlation effects play a negligible role. A density-based approach directly hinged on difference radial-density (DRD) distributions defined with respect the Hartree-Fock radial density has been employed for analyzing the impact of dynamic correlation effects on the density. Attention has been paid to the elimination of basis-set incompleteness errors. The DRD distributions calculated by several ab initio methods have been compared to their DFT counterparts generated for representatives of several generations of broadly used exchange-correlation functionals and for the recently developed orbital-dependent OEP2 exchange-correlation functional [Bartlett et al., J. Chem. Phys. 122, 034104 (2005)]. For the local, generalized-gradient, and hybrid functionals it has been found that the dynamic correlation effects are to a large extend accounted for by densities resulting from exchange-only calculations. Additional calculations with self-interaction corrected exchange potentials indicate that this finding cannot be explained as an artifact caused by the self-interaction error. It has been demonstrated that the VWN5 and LYP correlation functionals do not represent any substantial dynamical correlation effects on the electron density, whereas these effects are well represented by the orbital-dependent OEP2 correlation functional. Critical comparison of the present results with their counterparts reported in literature has been made. Some attention has been paid to demonstrating the differences between the energy- and density-based perspectives. They indicate the usefulness of density-based criteria for developing new exchange-correlation functionals. PMID:19405556
NASA Astrophysics Data System (ADS)
Jankowski, K.; Nowakowski, K.; Grabowski, I.; Wasilewski, J.
2009-04-01
The problem of linking the dynamic electron correlation effects defined in traditional ab initio methods [or wave function theories (WFTs)] with the structure of the individual density functional theory (DFT) exchange and correlation functionals has been analyzed for the Ne atom, for which nondynamic correlation effects play a negligible role. A density-based approach directly hinged on difference radial-density (DRD) distributions defined with respect the Hartree-Fock radial density has been employed for analyzing the impact of dynamic correlation effects on the density. Attention has been paid to the elimination of basis-set incompleteness errors. The DRD distributions calculated by several ab initio methods have been compared to their DFT counterparts generated for representatives of several generations of broadly used exchange-correlation functionals and for the recently developed orbital-dependent OEP2 exchange-correlation functional [Bartlett et al., J. Chem. Phys. 122, 034104 (2005)]. For the local, generalized-gradient, and hybrid functionals it has been found that the dynamic correlation effects are to a large extend accounted for by densities resulting from exchange-only calculations. Additional calculations with self-interaction corrected exchange potentials indicate that this finding cannot be explained as an artifact caused by the self-interaction error. It has been demonstrated that the VWN5 and LYP correlation functionals do not represent any substantial dynamical correlation effects on the electron density, whereas these effects are well represented by the orbital-dependent OEP2 correlation functional. Critical comparison of the present results with their counterparts reported in literature has been made. Some attention has been paid to demonstrating the differences between the energy- and density-based perspectives. They indicate the usefulness of density-based criteria for developing new exchange-correlation functionals.
Density functional calculations on model tyrosyl radicals.
Himo, F; Gräslund, A; Eriksson, L A
1997-01-01
A gradient-corrected density functional theory approach (PWP86) has been applied, together with large basis sets (IGLO-III), to investigate the structure and hyperfine properties of model tyrosyl free radicals. In nature, these radicals are observed in, e.g., the charge transfer pathways in photosystem II (PSII) and in ribonucleotide reductases (RNRs). By comparing spin density distributions and proton hyperfine couplings with experimental data, it is confirmed that the tyrosyl radicals present in the proteins are neutral. It is shown that hydrogen bonding to the phenoxyl oxygen atom, when present, causes a reduction in spin density on O and a corresponding increase on C4. Calculated proton hyperfine coupling constants for the beta-protons show that the alpha-carbon is rotated 75-80 degrees out of the plane of the ring in PSII and Salmonella typhimurium RNR, but only 20-30 degrees in, e.g., Escherichia coli, mouse, herpes simplex, and bacteriophage T4-induced RNRs. Furthermore, based on the present calculations, we have revised the empirical parameters used in the experimental determination of the oxygen spin density in the tyrosyl radical in E. coli RNR and of the ring carbon spin densities, from measured hyperfine coupling constants. Images FIGURE 1 FIGURE 5 PMID:9083661
Orbital-optimized density cumulant functional theory
Sokolov, Alexander Yu. Schaefer, Henry F.
2013-11-28
In density cumulant functional theory (DCFT) the electronic energy is evaluated from the one-particle density matrix and two-particle density cumulant, circumventing the computation of the wavefunction. To achieve this, the one-particle density matrix is decomposed exactly into the mean-field (idempotent) and correlation components. While the latter can be entirely derived from the density cumulant, the former must be obtained by choosing a specific set of orbitals. In the original DCFT formulation [W. Kutzelnigg, J. Chem. Phys. 125, 171101 (2006)] the orbitals were determined by diagonalizing the effective Fock operator, which introduces partial orbital relaxation. Here we present a new orbital-optimized formulation of DCFT where the energy is variationally minimized with respect to orbital rotations. This introduces important energy contributions and significantly improves the description of the dynamic correlation. In addition, it greatly simplifies the computation of analytic gradients, for which expressions are also presented. We offer a perturbative analysis of the new orbital stationarity conditions and benchmark their performance for a variety of chemical systems.
Density Functional Theory Models for Radiation Damage
NASA Astrophysics Data System (ADS)
Dudarev, S. L.
2013-07-01
Density functional theory models developed over the past decade provide unique information about the structure of nanoscale defects produced by irradiation and about the nature of short-range interaction between radiation defects, clustering of defects, and their migration pathways. These ab initio models, involving no experimental input parameters, appear to be as quantitatively accurate and informative as the most advanced experimental techniques developed for the observation of radiation damage phenomena. Density functional theory models have effectively created a new paradigm for the scientific investigation and assessment of radiation damage effects, offering new insight into the origin of temperature- and dose-dependent response of materials to irradiation, a problem of pivotal significance for applications.
Teaching Density Functional Theory Through Experiential Learning
NASA Astrophysics Data System (ADS)
Narasimhan, Shobhana
2015-09-01
Today, quantum mechanical density functional theory is often the method of choice for performing accurate calculations on atomic, molecular and condensed matter systems. Here, I share some of my experiences in teaching the necessary basics of solid state physics, as well as the theory and practice of density functional theory, in a number of workshops held in developing countries over the past two decades. I discuss the advantages of supplementing the usual mathematically formal teaching methods, characteristic of graduate courses, with the use of visual imagery and analogies. I also describe a successful experiment we carried out, which resulted in a joint publication co-authored by 67 lecturers and students participating in a summer school.
The problem of the universal density functional and the density matrix functional theory
Bobrov, V. B. Trigger, S. A.
2013-04-15
The analysis in this paper shows that the Hohenberg-Kohn theorem is the constellation of two statements: (i) the mathematically rigorous Hohenberg-Kohn lemma, which demonstrates that the same ground-state density cannot correspond to two different potentials of an external field, and (ii) the hypothesis of the existence of the universal density functional. Based on the obtained explicit expression for the nonrel-ativistic particle energy in a local external field, we prove that the energy of the system of more than two non-interacting electrons cannot be a functional of the inhomogeneous density. This result is generalized to the system of interacting electrons. It means that the Hohenberg-Kohn lemma cannot provide justification of the universal density functional for fermions. At the same time, statements of the density functional theory remain valid when considering any number of noninteracting ground-state bosons due to the Bose condensation effect. In the framework of the density matrix functional theory, the hypothesis of the existence of the universal density matrix functional corresponds to the cases of noninteracting particles and to interaction in the Hartree-Fock approximation.
Properties of the cosmological density distribution function
NASA Astrophysics Data System (ADS)
Bernardeau, Francis; Kofman, Lev
1995-04-01
The properties of the probability distribution function (PDF) of the cosmological continuous density field are studied. We focus our analysis on the quasi-linear regime where various calculations, based on dynamically motivated methods, have been presented: either by using the Zel'dovich approximation (ZA) or by using the perturbation theory to evaluate the behavior of the moments of the distribution function. We show how these two approaches are related to each other and that they can be used in a complementary way. For that respect, the one-dimensional dynamics, where the ZA is exact solution, has first been used as a testing ground. In particular, we show that, when the density PDF obtained with the ZA is regularized, its various moments exhibit the behavior expected by the perturbation theory applied to the ZA. We show that ZA approach can be used for arbitrary initial conditions (not only Gaussian) and that the nonlinear evolution of the moments can be obtained. The perturbation theory can be used for the exact dynamics. We take into account the final filtering of the density field both for ZA and perturbation theory. Applying these techniques, we got the generating function of the moments for the one-dimensional dynamics, the three-dimensional ZA, with and without smoothing effects. We also suggest methods to build PDFs. One is based on the Laplace inverse transform of the moment generating function. The other, the Edgeworth expansion, is obtained when the previous generating function is truncated at a given order and allows evaluation of the PDF out of limited number of moments. It provides insight on the relationship between the moments and the shape of the density PDF. In particular, it provides an alternative method to evaluate the skewness and kurtosis by measuring the PDF around its maximum. Eventually, results obtained from a numerical simulation with cold dark matter initial conditions have been used to validate the accuracy of the considered
Magnetic susceptibility of semiconductors by an all-electron first-principles approach
Ohno, K. |; Mauri, F.; Louie, S.G. |
1997-07-01
The magnetic susceptibility ({chi}) of the semiconductors (diamond, Si, GaAs, and GaP) and of the inert-gas solids (Ne, Ar, and Kr) are evaluated within density-functional theory in the local-density approximation, using a mixed-basis all-electron approach. In Si, GaAs, GaP, Ar, and Kr, the contribution of core electrons to {chi} is comparable to that of valence electrons. However, our results show that the contribution associated with the core states is independent of the chemical environment and can be computed from the isolated atoms. Moreover, our results indicate that the use of a {open_quotes}scissor operator{close_quotes} does not improve the agreement of the theoretical {chi} with experiments. {copyright} {ital 1997} {ital The American Physical Society}
Pseudospectral time-dependent density functional theory
NASA Astrophysics Data System (ADS)
Ko, Chaehyuk; Malick, David K.; Braden, Dale A.; Friesner, Richard A.; Martínez, Todd J.
2008-03-01
Time-dependent density functional theory (TDDFT) is implemented within the Tamm-Dancoff approximation (TDA) using a pseudospectral approach to evaluate two-electron repulsion integrals. The pseudospectral approximation uses a split representation with both spectral basis functions and a physical space grid to achieve a reduction in the scaling behavior of electronic structure methods. We demonstrate here that exceptionally sparse grids may be used in the excitation energy calculation, following earlier work employing the pseudospectral approximation for determining correlation energies in wavefunction-based methods with similar conclusions. The pseudospectral TDA-TDDFT method is shown to be up to ten times faster than a conventional algorithm for hybrid functionals without sacrificing chemical accuracy.
Optimization of constrained density functional theory
NASA Astrophysics Data System (ADS)
O'Regan, David D.; Teobaldi, Gilberto
2016-07-01
Constrained density functional theory (cDFT) is a versatile electronic structure method that enables ground-state calculations to be performed subject to physical constraints. It thereby broadens their applicability and utility. Automated Lagrange multiplier optimization is necessary for multiple constraints to be applied efficiently in cDFT, for it to be used in tandem with geometry optimization, or with molecular dynamics. In order to facilitate this, we comprehensively develop the connection between cDFT energy derivatives and response functions, providing a rigorous assessment of the uniqueness and character of cDFT stationary points while accounting for electronic interactions and screening. In particular, we provide a nonperturbative proof that stable stationary points of linear density constraints occur only at energy maxima with respect to their Lagrange multipliers. We show that multiple solutions, hysteresis, and energy discontinuities may occur in cDFT. Expressions are derived, in terms of convenient by-products of cDFT optimization, for quantities such as the dielectric function and a condition number quantifying ill definition in multiple constraint cDFT.
Recent progress in density functional theory
NASA Astrophysics Data System (ADS)
Truhlar, Donald
2014-03-01
Ongoing work involves several areas of density functional theory: new methods for computing electronic excitation energies, including a new way to remove spin contamination in the spin-flip Tamm-Dancoff approximation and a configuration-interaction-corrected Tamm-Dancoff Approximation for treating conical intersections; new ways to treat open-shell states, including a reinterpreted broken-symmetry method and multi-configuration Kohn-Sham theory; a new exchange-correlation functional; new tests of density functional theory against databases for electronic transition energies and molecules and solids containing metal atoms; and applications. A selection of results will be presented. I am grateful to the following collaborators for contributions to the ongoing work: Boris Averkiev, Rebecca Carlson, Laura Fernandez, Laura Gagliardi, Chad Hoyer, Francesc Illas, Miho Isegawa, Shaohong Li, Giovanni Li Manni, Sijie Luo, Dongxia Ma, Remi Maurice, Rubén Means-Pañeda, Roberto Peverati, Nora Planas, Prasenjit Seal, Pragya Verma, Bo Wang, Xuefei Xu, Ke R. Yang, Haoyu Yu, Wenjing Zhang, and Jingjing Zheng. Supported in part by the AFOSR and U.S. DOE.
Modulation Based on Probability Density Functions
NASA Technical Reports Server (NTRS)
Williams, Glenn L.
2009-01-01
A proposed method of modulating a sinusoidal carrier signal to convey digital information involves the use of histograms representing probability density functions (PDFs) that characterize samples of the signal waveform. The method is based partly on the observation that when a waveform is sampled (whether by analog or digital means) over a time interval at least as long as one half cycle of the waveform, the samples can be sorted by frequency of occurrence, thereby constructing a histogram representing a PDF of the waveform during that time interval.
Adiabatic corrections to density functional theory energies and wave functions.
Mohallem, José R; Coura, Thiago de O; Diniz, Leonardo G; de Castro, Gustavo; Assafrão, Denise; Heine, Thomas
2008-09-25
The adiabatic finite-nuclear-mass-correction (FNMC) to the electronic energies and wave functions of atoms and molecules is formulated for density-functional theory and implemented in the deMon code. The approach is tested for a series of local and gradient corrected density functionals, using MP2 results and diagonal-Born-Oppenheimer corrections from the literature for comparison. In the evaluation of absolute energy corrections of nonorganic molecules the LDA PZ81 functional works surprisingly better than the others. For organic molecules the GGA BLYP functional has the best performance. FNMC with GGA functionals, mainly BLYP, show a good performance in the evaluation of relative corrections, except for nonorganic molecules containing H atoms. The PW86 functional stands out with the best evaluation of the barrier of linearity of H2O and the isotopic dipole moment of HDO. In general, DFT functionals display an accuracy superior than the common belief and because the corrections are based on a change of the electronic kinetic energy they are here ranked in a new appropriate way. The approach is applied to obtain the adiabatic correction for full atomization of alcanes C(n)H(2n+2), n = 4-10. The barrier of 1 mHartree is approached for adiabatic corrections, justifying its insertion into DFT. PMID:18537228
NASA Astrophysics Data System (ADS)
Sicilia, E.; de Luca, G.; Chiodo, S.; Russo, N.; Calaminici, P.; Koster, A. M.; Jug, K.
Density functional calculations of the electric field gradient tensor at the nitrogen nucleus in 13 test molecules, containing 14 nitrogen sites, have been performed using the linear combination of Gaussian-type orbital Kohn-Sham density functional theory (LCGTO-KSDFT) approach. Local and gradient corrected functionals were used for all-electron calculations. All the molecular structures were optimized at their respective levels of theory with extended basis sets. Calibrated 14N nuclear quadrupole moments were obtained through a fitting procedure between calculated electric field gradients and experimental nuclear quadrupole coupling constants of the test set of molecules for each basis set and functional considered. With these calibrated 14N nuclear quadrupole moments, the nuclear quadrupole coupling constants of the following selected systems were determined: fluoromethylisonitrile, pyridine, pyrrole, imadazole, pyrazole, 1,8-bis(dimethyl-amino)naphthalene, cyclotetramethylenetetranitramine, cocaine and heroin.
Gaussian basis density functional theory for systems periodic in two or three dimensions
Hess, A.C.; Lin, Zijing; Clerc, D.G.
1996-12-31
We will present the formulation and results of a new, fully self-consistent all electron density functional theory that utilizes localized Gaussian basis functions to treat systems possessing 3- and 2- dimensional periodicity. Our method extends, in a fully rigorous fashion, many of the concepts commonly found in molecular density functional theories and can accurately be described as an {open_quotes}ab initio or first principles{close_quotes} approach. Results will be presented for several illustrative spin paired and unpaired insulating and semi-conducting bulk crystalline systems. The effect of employing local and non-local exchange and correlation functionals on the geometric, elastic, and electronic properties of diamond, silicon, silicon carbide, magnesium oxide and beryllium oxide will also be presented. Finally, the geometric and electronic structure of several oxide and semi-conducting surfaces will also be presented.
Density-functional theory of superconductivity
NASA Astrophysics Data System (ADS)
Gross, E. K. U.
2008-03-01
A prominent challenge of modern condensed-matter theory is to predict reliably material-specific properties of superconductors, such as the critical temperature. The traditional model of Bardeen, Cooper and Schrieffer (BCS) properly describes the universal features that all conventional superconductors have in common, but it is not able to make accurate predictions of material-specific properties. To tackle this problem, a density-functional formalism has been developed [1] which describes superconductors in thermal equilibrium in terms of three quantities: the ordinary density, the superconducting order parameter, and the nuclear N-body density. These three ``densities'' are determined self-consistently through a set of Kohn-Sham equations. Approximations of the universal exchange-correlation functional are derived on the basis of many-body perturbation theory. In this way, a true ab-initio description is achieved which does not contain any adjustable parameters such as the μ* of Eliashberg theory. Numerical results for the critical temperature, the isotope effect, the gap function and the jump of the specific heat will be presented for simple metals, for MgB2 [2] and CaBeSi, and for calcium intercalated graphite (CaC6) [3]. Furthermore, results for Li, Al, K, and H under pressure will be discussed. The calculations explain why Li and Al behave very differently, leading to a strong enhancement of superconductivity for Li and to a clear suppression for Al with increasing pressure [4]. For K we predict a behavior similar to Li, i.e. a strong increase of Tc with increasing pressure. Finally, hydrogen is found to be a three-gap superconductor whose critical temperature increases with increasing pressure until about 100K (at 500 GPa). [1] M. Lüders, M.A.L. Marques, N.N. Lathiotakis, A. Floris,G. Profeta, L. Fast, A.Continenza, S. Massidda, E.K.U. Gross, PRB 72, 024545 (2005). [2] A. Floris, G. Profeta, N.N. Lathiotakis, M. Lüders, M.A.L. Marques, C. Franchini, E
Local spin analyses using density functional theory
NASA Astrophysics Data System (ADS)
Abate, Bayileyegn; Peralta, Juan
Local spin analysis is a valuable technique in computational investigations magnetic interactions on mono- and polynuclear transition metal complexes, which play vital roles in catalysis, molecular magnetism, artificial photosynthesis, and several other commercially important materials. The relative size and complex electronic structure of transition metal complexes often prohibits the use of multi-determinant approaches, and hence, practical calculations are often limited to single-determinant methods. Density functional theory (DFT) has become one of the most successful and widely used computational tools for the electronic structure study of complex chemical systems; transition metal complexes in particular. Within the DFT formalism, a more flexible and complete theoretical modeling of transition metal complexes can be achieved by considering noncollinear spins, in which the spin density is 'allowed to' adopt noncollinear structures in stead of being constrained to align parallel/antiparallel to a universal axis of magnetization. In this meeting, I will present local spin analyses results obtained using different DFT functionals. Local projection operators are used to decompose the expectation value
Chemistry by Way of Density Functional Theory
NASA Technical Reports Server (NTRS)
Bauschlicher, Charles W., Jr.; Ricca, Alessandra; Partridge, Harry; Langohff, Stephen R.; Arnold, James O. (Technical Monitor)
1996-01-01
In this work we demonstrate that density functional theory (DFT) methods make an important contribution to understanding chemical systems and are an important additional method for the computational chemist. We report calibration calculations obtained with different functionals for the 55 G2 molecules to justify our selection of the B3LYP functional. We show that accurate geometries and vibrational frequencies obtained at the B3LYP level can be combined with traditional methods to simplify the calculation of accurate heats of formation. We illustrate the application of the B3LYP approach to a variety of chemical problems from the vibrational frequencies of polycyclic aromatic hydrocarbons to transition metal systems. We show that the B3LYP method typically performs better than the MP2 method at a significantly lower computational cost. Thus the B3LYP method allows us to extend our studies to much larger systems while maintaining a high degree of accuracy. We show that for transition metal systems, the B3LYP bond energies are typically of sufficient accuracy that they can be used to explain experimental trends and even differentiate between different experimental values. We show that for boron clusters the B3LYP energetics are not as good as for many of the other systems presented, but even in this case the B3LYP approach is able to help understand the experimental trends.
Density functional studies of representative pericyclic reactions
NASA Astrophysics Data System (ADS)
Carpenter, John E.; Sosa, Carlos P.
1994-07-01
Density functional theory (DFT) has traditionally been shunned by computational chemists, but has long seen widespread use in the physics community. Recently, however, DFT has been adopted by the ab initio quantum chemistry community and much activity has been devoted to refining the methodology and exploring the range of its applicability. We investigate the use of DFT (both local (LDF) and non-local (NLDF) spin density approximations) to calculate transition and equilibrium structures for three representative pericyclic reactions: the electrocyclic ring opening reaction of cyclobutene, the [1,5] sigmatropic hydrogen shift reaction in (Z)-1,3-pentadiene, and the Diels-Alder cycloaddition reaction between ethylene and butadiene. LDF theory tends to overemphasize the stability of the ringed structures in each of these reactions. For example, LDF predicts a very low (6 kcal mol -1) barrier to reaction for the Deils-Alder reaction. NLDF theory substantially improves the calculated reaction barrier (20 kcal mol -1), but it is still low with respect to experiment.
Semiconductor Thermochemistry in Density Functional Calculations
Lany, S.
2008-01-01
The local-density and generalized gradient approximations (LDA and GGA) to density functional theory (DFT) exhibit incomplete error cancellation when energy differences are taken between chemically dissimilar systems. This energy inconsistency is manifested, e.g., in the tendency to underestimate the heat (enthalpy) of formation of semiconducting and insulating compounds in LDA and, even more so, in GGA. Considering a set of 61 compounds that can be formed from 14 elements (cations: Cu, Mg, Ca, Zn, Cd, Al, Ga, and In; anions: N, P, As, O, S, and Se), optimized elemental reference energies are determined by least-squares error minimization of an overdetermined set of linear equations. These elemental energies are 'optimally consistent' with the DFT energies of the semiconductor compounds and imply corrections of up to 1 eV compared to the respective LDA or GGA energies. While these 'corrections' are not to be understood to yield the correct absolute total energies of the elements, they are proposed to give appropriate bounds for the chemical potentials for thermodynamic processes in semiconductors and insulators, such as, e.g., defect formation, surface reconstruction, or catalytic processes. The present model allows to evaluate thermodynamic processes using DFT energy differences taken only between systems that are expected to show good error cancellation.
Carrier Modulation Via Waveform Probability Density Function
NASA Technical Reports Server (NTRS)
Williams, Glenn L.
2004-01-01
Beyond the classic modes of carrier modulation by varying amplitude (AM), phase (PM), or frequency (FM), we extend the modulation domain of an analog carrier signal to include a class of general modulations which are distinguished by their probability density function histogram. Separate waveform states are easily created by varying the pdf of the transmitted waveform. Individual waveform states are assignable as proxies for digital ONEs or ZEROs. At the receiver, these states are easily detected by accumulating sampled waveform statistics and performing periodic pattern matching, correlation, or statistical filtering. No fundamental natural laws are broken in the detection process. We show how a typical modulation scheme would work in the digital domain and suggest how to build an analog version. We propose that clever variations of the modulating waveform (and thus the histogram) can provide simple steganographic encoding.
Carrier Modulation Via Waveform Probability Density Function
NASA Technical Reports Server (NTRS)
Williams, Glenn L.
2006-01-01
Beyond the classic modes of carrier modulation by varying amplitude (AM), phase (PM), or frequency (FM), we extend the modulation domain of an analog carrier signal to include a class of general modulations which are distinguished by their probability density function histogram. Separate waveform states are easily created by varying the pdf of the transmitted waveform. Individual waveform states are assignable as proxies for digital one's or zero's. At the receiver, these states are easily detected by accumulating sampled waveform statistics and performing periodic pattern matching, correlation, or statistical filtering. No fundamental physical laws are broken in the detection process. We show how a typical modulation scheme would work in the digital domain and suggest how to build an analog version. We propose that clever variations of the modulating waveform (and thus the histogram) can provide simple steganographic encoding.
Phases of Polonium via Density Functional Theory
NASA Astrophysics Data System (ADS)
Verstraete, Matthieu J.
2010-01-01
The thermodynamical properties of the main phases of metallic polonium are examined using density functional theory. The exceptional nature of the solid-solid phase transition of α to β Po is underlined: it induces a lowering in symmetry, from cubic to rhombohedral, with increasing temperature. This is explained as the result of a delicate balance between bonding and entropic effects. Overall agreement with existing experimental data is good by state-of-the-art standards. The phonons of Po present Kohn anomalies, and it is shown that the effect of spin-orbit interactions is the inverse of that in normal metals: due to the nonspherical nature of the Fermi Surface, spin-orbit effects reduce nesting and harden most phonon frequencies.
Effective potential in density matrix functional theory.
Nagy, A; Amovilli, C
2004-10-01
In the previous paper it was shown that in the ground state the diagonal of the spin independent second-order density matrix n can be determined by solving a single auxiliary equation of a two-particle problem. Thus the problem of an arbitrary system with even electrons can be reduced to a two-particle problem. The effective potential of the two-particle equation contains a term v(p) of completely kinetic origin. Virial theorem and hierarchy of equations are derived for v(p) and simple approximations are proposed. A relationship between the effective potential u(p) of the shape function equation and the potential v(p) is established. PMID:15473719
Improving Density Functionals with Quantum Harmonic Oscillators
NASA Astrophysics Data System (ADS)
Tkatchenko, Alexandre
2013-03-01
Density functional theory (DFT) is the most widely used and successful approach for electronic structure calculations. However, one of the pressing challenges for DFT is developing efficient functionals that can accurately capture the omnipresent long-range electron correlations, which determine the structure and stability of many molecules and materials. Here we show that, under certain conditions, the problem of computing the long-range correlation energy of interacting electrons can be mapped to a system of coupled quantum harmonic oscillators (QHOs). The proposed model allows us to synergistically combine concepts from DFT, quantum chemistry, and the widely discussed random-phase approximation for the correlation energy. In the dipole limit, the interaction energy for a system of coupled QHOs can be calculated exactly, thereby leading to an efficient and accurate model for the many-body dispersion energy of complex molecules and materials. The studied examples include intermolecular binding energies, the conformational hierarchy of DNA structures, the geometry and stability of molecular crystals, and supramolecular host-guest complexes (A. Tkatchenko, R. A. DiStasio Jr., R. Car, M. Scheffler, Phys. Rev. Lett. 108, 236402 (2012); R. A. DiStasio Jr., A. von Lilienfeld, A. Tkatchenko, PNAS 109, 14791 (2012); A. Tkatchenko, D. Alfe, K. S. Kim, J. Chem. Theory and Comp. (2012), doi: 10.1021/ct300711r; A. Tkatchenko, A. Ambrosetti, R. A. DiStasio Jr., arXiv:1210.8343v1).
Building a Universal Nuclear Energy Density Functional
Carlson, Joe A.; Furnstahl, Dick; Horoi, Mihai; Lust, Rusty; Nazaewicc, Witek; Ng, Esmond; Thompson, Ian; Vary, James
2012-12-30
During the period of Dec. 1 2006 – Jun. 30, 2012, the UNEDF collaboration carried out a comprehensive study of all nuclei, based on the most accurate knowledge of the strong nuclear interaction, the most reliable theoretical approaches, the most advanced algorithms, and extensive computational resources, with a view towards scaling to the petaflop platforms and beyond. The long-term vision initiated with UNEDF is to arrive at a comprehensive, quantitative, and unified description of nuclei and their reactions, grounded in the fundamental interactions between the constituent nucleons. We seek to replace current phenomenological models of nuclear structure and reactions with a well-founded microscopic theory that delivers maximum predictive power with well-quantified uncertainties. Specifically, the mission of this project has been three-fold: First, to find an optimal energy density functional (EDF) using all our knowledge of the nucleonic Hamiltonian and basic nuclear properties; Second, to apply the EDF theory and its extensions to validate the functional using all the available relevant nuclear structure and reaction data; Third, to apply the validated theory to properties of interest that cannot be measured, in particular the properties needed for reaction theory.
A density functional for sparse matter
NASA Astrophysics Data System (ADS)
Langreth, D. C.; Lundqvist, B. I.; Chakarova-Käck, S. D.; Cooper, V. R.; Dion, M.; Hyldgaard, P.; Kelkkanen, A.; Kleis, J.; Kong, Lingzhu; Li, Shen; Moses, P. G.; Murray, E.; Puzder, A.; Rydberg, H.; Schröder, E.; Thonhauser, T.
2009-02-01
Sparse matter is abundant and has both strong local bonds and weak nonbonding forces, in particular nonlocal van der Waals (vdW) forces between atoms separated by empty space. It encompasses a broad spectrum of systems, like soft matter, adsorption systems and biostructures. Density-functional theory (DFT), long since proven successful for dense matter, seems now to have come to a point, where useful extensions to sparse matter are available. In particular, a functional form, vdW-DF (Dion et al 2004 Phys. Rev. Lett. 92 246401; Thonhauser et al 2007 Phys. Rev. B 76 125112), has been proposed for the nonlocal correlations between electrons and applied to various relevant molecules and materials, including to those layered systems like graphite, boron nitride and molybdenum sulfide, to dimers of benzene, polycyclic aromatic hydrocarbons (PAHs), doped benzene, cytosine and DNA base pairs, to nonbonding forces in molecules, to adsorbed molecules, like benzene, naphthalene, phenol and adenine on graphite, alumina and metals, to polymer and carbon nanotube (CNT) crystals, and hydrogen storage in graphite and metal-organic frameworks (MOFs), and to the structure of DNA and of DNA with intercalators. Comparison with results from wavefunction calculations for the smaller systems and with experimental data for the extended ones show the vdW-DF path to be promising. This could have great ramifications.
Semiclassical origins of density functional theory
NASA Astrophysics Data System (ADS)
Burke, Kieron
2009-03-01
Until the seminal work of Hohenberg, Kohn, and Sham of the mid 60's, most density functional theory (DFT) was derived from semiclassical approximations. This non-empirical approach shows an intrinsic difference between solids (for which DFT was originally developed) and molecules, and explains many of its more mysterious manifestations. For example, the success of DFT for molecules has nothing to do with the uniform gas. Results include [1] a derivation of the empirical parameter in the B88 exchange functional, [2] PBEsol, a new GGA that restores the exchange gradient expansion and improves lattice constants in solids, [3] a novel approach to ``orbital-free'' DFT that, in preliminary tests, is 40 times more accurate than its DFT counterpart. The talk is aimed at a general theoretical audience. Detailed technical knowledge of DFT is neither needed, nor desirable. [4pt] [1] J.P. Perdew, L.A. Constantin, E. Sagvolden, and KB, Phys. Rev. Lett. 97, 223002 (2006). [0pt] [2] J.P. Perdew, A. Ruzsinszky, G.I. Csonka, O.A. Vydrov, G.E. Scuseria, L.A. Constantin, X. Zhou, and KB, Phys. Rev. Lett. 100, 136406 (2008). [0pt] [3] Peter Elliott, Donghyung Lee, Attila Cangi, KB, Phys. Rev. Lett. 100, 256406 (2008).
Rationale for switching to nonlocal functionals in density functional theory
NASA Astrophysics Data System (ADS)
Lazić, P.; Atodiresei, N.; Caciuc, V.; Brako, R.; Gumhalter, B.; Blügel, S.
2012-10-01
Density functional theory (DFT) has been steadily improving over the past few decades, becoming the standard tool for electronic structure calculations. The early local functionals (LDA) were eventually replaced by more accurate semilocal functionals (GGA) which are in use today. A major persisting drawback is the lack of the nonlocal correlation which is at the core of dispersive (van der Waals) forces, so that a large and important class of systems remains outside the scope of DFT. The vdW-DF correlation functional of Langreth and Lundqvist, published in 2004, was the first nonlocal functional which could be easily implemented. Beyond expectations, the nonlocal functional has brought significant improvement to systems that were believed not to be sensitive to nonlocal correlations. In this paper, we use the example of graphene nanodomes growing on the Ir(111) surface, where with an increase of the size of the graphene islands the character of the bonding changes from strong chemisorption towards almost pure physisorption. We demonstrate how the seamless character of the vdW-DF functionals makes it possible to treat all regimes self-consistently, proving to be a systematic and consistent improvement of DFT regardless of the nature of bonding. We also discuss the typical surface science example of CO adsorption on (111) surfaces of metals, which shows that the nonlocal correlation may also be crucial for strongly chemisorbed systems. We briefly discuss open questions, in particular the choice of the most appropriate exchange part of the functional. As the vdW-DF begins to appear implemented self-consistently in a number of popular DFT codes, with numerical costs close to the GGA calculations, we draw the attention of the DFT community to the advantages and benefits of the adoption of this new class of functionals.
Density Functional Theory study of the equilibrium density of water at normal conditions
NASA Astrophysics Data System (ADS)
Wang, Jue; Roman-Perez, Guillermo; Soler, Jose M.; Artacho, Emilio; Fernandez-Serra, Marivi
2010-03-01
Ab initio molecular dynamics of liquid water with the use of density functional theory (DFT) currently underperform experimental equilibrium density 1g/cm^3 under room temperature. At constant density, not much is known about the equilibrium density of commonly used GGA functionals in liquid water simulations. We present a DFT-based AIMD study of liquid water at different densities and analyze the structure and diffusivity of water with different exchange and correlation functionals. We show that all current GGA functionals fail to reproduce experimental density, however, the explicit description of long range correlations through a Van der Walls density functional (DRSLL)footnotetextM. Dion, H. Rydberg, E. Schr"oder, D. C. Langreth, and B. I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004) can potentially transform our current understanding of the structure of liquid water. Our results shows that this new functional improves density, with only 2% error to experiment. But it underperforms GGA functionals in terms of structure.
Embedded-cluster calculations in a numeric atomic orbital density-functional theory framework
Berger, Daniel Oberhofer, Harald; Reuter, Karsten; Logsdail, Andrew J. Farrow, Matthew R.; Catlow, C. Richard A.; Sokol, Alexey A.; Sherwood, Paul; Blum, Volker
2014-07-14
We integrate the all-electron electronic structure code FHI-aims into the general ChemShell package for solid-state embedding quantum and molecular mechanical (QM/MM) calculations. A major undertaking in this integration is the implementation of pseudopotential functionality into FHI-aims to describe cations at the QM/MM boundary through effective core potentials and therewith prevent spurious overpolarization of the electronic density. Based on numeric atomic orbital basis sets, FHI-aims offers particularly efficient access to exact exchange and second order perturbation theory, rendering the established QM/MM setup an ideal tool for hybrid and double-hybrid level density functional theory calculations of solid systems. We illustrate this capability by calculating the reduction potential of Fe in the Fe-substituted ZSM-5 zeolitic framework and the reaction energy profile for (photo-)catalytic water oxidation at TiO{sub 2}(110)
Flexoelectricity from density-functional perturbation theory
NASA Astrophysics Data System (ADS)
Stengel, Massimiliano
2013-11-01
We derive the complete flexoelectric tensor, including electronic and lattice-mediated effects, of an arbitrary insulator in terms of the microscopic linear response of the crystal to atomic displacements. The basic ingredient, which can be readily calculated from first principles in the framework of density-functional perturbation theory, is the quantum-mechanical probability current response to a long-wavelength acoustic phonon. Its second-order Taylor expansion in the wave vector q around the Γ (q=0) point in the Brillouin zone naturally yields the flexoelectric tensor. At order one in q we recover Martin's theory of piezoelectricity [Martin, Phys. Rev. B 5, 1607 (1972)], thus providing an alternative derivation thereof. To put our derivations on firm theoretical grounds, we perform a thorough analysis of the nonanalytic behavior of the dynamical matrix and other response functions in a vicinity of Γ. Based on this analysis, we find that there is an ambiguity in the specification of the “zero macroscopic field” condition in the flexoelectric case; such arbitrariness can be related to an analytic band-structure term, in close analogy to the theory of deformation potentials. As a by-product, we derive a rigorous generalization of the Cochran-Cowley formula [Cochran and Cowley, J. Phys. Chem. Solids 23, 447 (1962)] to higher orders in q. This can be of great utility in building reliable atomistic models of electromechanical phenomena, as well as for improving the accuracy of the calculation of phonon dispersion curves. Finally, we discuss the physical interpretation of the various contributions to the flexoelectric response, either in the static or dynamic regime, and we relate our findings to earlier theoretical works on the subject.
Bone mineral density, adiposity, and cognitive functions
Sohrabi, Hamid R.; Bates, Kristyn A.; Weinborn, Michael; Bucks, Romola S.; Rainey-Smith, Stephanie R.; Rodrigues, Mark A.; Bird, Sabine M.; Brown, Belinda M.; Beilby, John; Howard, Matthew; Criddle, Arthur; Wraith, Megan; Taddei, Kevin; Martins, Georgia; Paton, Athena; Shah, Tejal; Dhaliwal, Satvinder S.; Mehta, Pankaj D.; Foster, Jonathan K.; Martins, Ian J.; Lautenschlager, Nicola T.; Mastaglia, Francis; Laws, Simon M.; Martins, Ralph N.
2015-01-01
Cognitive decline and dementia due to Alzheimer's disease (AD) have been associated with genetic, lifestyle, and environmental factors. A number of potentially modifiable risk factors should be taken into account when preventive or ameliorative interventions targeting dementia and its preclinical stages are investigated. Bone mineral density (BMD) and body composition are two such potentially modifiable risk factors, and their association with cognitive decline was investigated in this study. 164 participants, aged 34–87 years old (62.78 ± 9.27), were recruited for this longitudinal study and underwent cognitive and clinical examinations at baseline and after 3 years. Blood samples were collected for apolipoprotein E (APOE) genotyping and dual energy x-ray absorptiometry (DXA) was conducted at the same day as cognitive assessment. Using hierarchical regression analysis, we found that BMD and lean body mass, as measured using DXA were significant predictors of episodic memory. Age, gender, APOE status, and premorbid IQ were controlled for. Specifically, the List A learning from California Verbal Learning Test was significantly associated with BMD and lean mass both at baseline and at follow up assessment. Our findings indicate that there is a significant association between BMD and lean body mass and episodic verbal learning. While the involvement of modifiable lifestyle factors in human cognitive function has been examined in different studies, there is a need for further research to understand the potential underlying mechanisms. PMID:25741279
Bone mineral density, adiposity, and cognitive functions.
Sohrabi, Hamid R; Bates, Kristyn A; Weinborn, Michael; Bucks, Romola S; Rainey-Smith, Stephanie R; Rodrigues, Mark A; Bird, Sabine M; Brown, Belinda M; Beilby, John; Howard, Matthew; Criddle, Arthur; Wraith, Megan; Taddei, Kevin; Martins, Georgia; Paton, Athena; Shah, Tejal; Dhaliwal, Satvinder S; Mehta, Pankaj D; Foster, Jonathan K; Martins, Ian J; Lautenschlager, Nicola T; Mastaglia, Francis; Laws, Simon M; Martins, Ralph N
2015-01-01
Cognitive decline and dementia due to Alzheimer's disease (AD) have been associated with genetic, lifestyle, and environmental factors. A number of potentially modifiable risk factors should be taken into account when preventive or ameliorative interventions targeting dementia and its preclinical stages are investigated. Bone mineral density (BMD) and body composition are two such potentially modifiable risk factors, and their association with cognitive decline was investigated in this study. 164 participants, aged 34-87 years old (62.78 ± 9.27), were recruited for this longitudinal study and underwent cognitive and clinical examinations at baseline and after 3 years. Blood samples were collected for apolipoprotein E (APOE) genotyping and dual energy x-ray absorptiometry (DXA) was conducted at the same day as cognitive assessment. Using hierarchical regression analysis, we found that BMD and lean body mass, as measured using DXA were significant predictors of episodic memory. Age, gender, APOE status, and premorbid IQ were controlled for. Specifically, the List A learning from California Verbal Learning Test was significantly associated with BMD and lean mass both at baseline and at follow up assessment. Our findings indicate that there is a significant association between BMD and lean body mass and episodic verbal learning. While the involvement of modifiable lifestyle factors in human cognitive function has been examined in different studies, there is a need for further research to understand the potential underlying mechanisms. PMID:25741279
Density functional theory in the solid state
Hasnip, Philip J.; Refson, Keith; Probert, Matt I. J.; Yates, Jonathan R.; Clark, Stewart J.; Pickard, Chris J.
2014-01-01
Density functional theory (DFT) has been used in many fields of the physical sciences, but none so successfully as in the solid state. From its origins in condensed matter physics, it has expanded into materials science, high-pressure physics and mineralogy, solid-state chemistry and more, powering entire computational subdisciplines. Modern DFT simulation codes can calculate a vast range of structural, chemical, optical, spectroscopic, elastic, vibrational and thermodynamic phenomena. The ability to predict structure–property relationships has revolutionized experimental fields, such as vibrational and solid-state NMR spectroscopy, where it is the primary method to analyse and interpret experimental spectra. In semiconductor physics, great progress has been made in the electronic structure of bulk and defect states despite the severe challenges presented by the description of excited states. Studies are no longer restricted to known crystallographic structures. DFT is increasingly used as an exploratory tool for materials discovery and computational experiments, culminating in ex nihilo crystal structure prediction, which addresses the long-standing difficult problem of how to predict crystal structure polymorphs from nothing but a specified chemical composition. We present an overview of the capabilities of solid-state DFT simulations in all of these topics, illustrated with recent examples using the CASTEP computer program. PMID:24516184
Photostriction in Ferroelectrics from Density Functional Theory
NASA Astrophysics Data System (ADS)
Paillard, Charles; Xu, Bin; Dkhil, Brahim; Geneste, Grégory; Bellaiche, L.
2016-06-01
An ab initio procedure allowing the computation of the deformation of ferroelectric-based materials under light is presented. This numerical scheme consists in structurally relaxing the system under the constraint of a fixed ne concentration of electrons photoexcited into a specific conduction band edge state from a chosen valence band state, via the use of a constrained density functional theory method. The resulting change in lattice constant along a selected crystallographic direction is then calculated for a reasonable estimate of ne. This method is applied to bulk multiferroic BiFeO3 and predicts a photostriction effect of the same order of magnitude than the ones recently observed. A strong dependence of photostrictive response on both the reached conduction state and the crystallographic direction (along which this effect is determined) is also revealed. Furthermore, analysis of the results demonstrates that the photostriction mechanism mostly originates from the screening of the spontaneous polarization by the photoexcited electrons in combination with the inverse piezoelectric effect.
Dynamical density functional theory for microswimmers
NASA Astrophysics Data System (ADS)
Menzel, Andreas M.; Saha, Arnab; Hoell, Christian; Löwen, Hartmut
2016-01-01
Dynamical density functional theory (DDFT) has been successfully derived and applied to describe on one hand passive colloidal suspensions, including hydrodynamic interactions between individual particles. On the other hand, active "dry" crowds of self-propelled particles have been characterized using DDFT. Here, we go one essential step further and combine these two approaches. We establish a DDFT for active microswimmer suspensions. For this purpose, simple minimal model microswimmers are introduced. These microswimmers self-propel by setting the surrounding fluid into motion. They hydrodynamically interact with each other through their actively self-induced fluid flows and via the common "passive" hydrodynamic interactions. An effective soft steric repulsion is also taken into account. We derive the DDFT starting from common statistical approaches. Our DDFT is then tested and applied by characterizing a suspension of microswimmers, the motion of which is restricted to a plane within a three-dimensional bulk fluid. Moreover, the swimmers are confined by a radially symmetric trapping potential. In certain parameter ranges, we find rotational symmetry breaking in combination with the formation of a "hydrodynamic pumping state," which has previously been observed in the literature as a result of particle-based simulations. An additional instability of this pumping state is revealed.
Photostriction in Ferroelectrics from Density Functional Theory.
Paillard, Charles; Xu, Bin; Dkhil, Brahim; Geneste, Grégory; Bellaiche, L
2016-06-17
An ab initio procedure allowing the computation of the deformation of ferroelectric-based materials under light is presented. This numerical scheme consists in structurally relaxing the system under the constraint of a fixed n_{e} concentration of electrons photoexcited into a specific conduction band edge state from a chosen valence band state, via the use of a constrained density functional theory method. The resulting change in lattice constant along a selected crystallographic direction is then calculated for a reasonable estimate of n_{e}. This method is applied to bulk multiferroic BiFeO_{3} and predicts a photostriction effect of the same order of magnitude than the ones recently observed. A strong dependence of photostrictive response on both the reached conduction state and the crystallographic direction (along which this effect is determined) is also revealed. Furthermore, analysis of the results demonstrates that the photostriction mechanism mostly originates from the screening of the spontaneous polarization by the photoexcited electrons in combination with the inverse piezoelectric effect. PMID:27367406
The Nuclear Energy Density Functional Formalism
NASA Astrophysics Data System (ADS)
Duguet, T.
The present document focuses on the theoretical foundations of the nuclear energy density functional (EDF) method. As such, it does not aim at reviewing the status of the field, at covering all possible ramifications of the approach or at presenting recent achievements and applications. The objective is to provide a modern account of the nuclear EDF formalism that is at variance with traditional presentations that rely, at one point or another, on a Hamiltonian-based picture. The latter is not general enough to encompass what the nuclear EDF method represents as of today. Specifically, the traditional Hamiltonian-based picture does not allow one to grasp the difficulties associated with the fact that currently available parametrizations of the energy kernel E[g',g] at play in the method do not derive from a genuine Hamilton operator, would the latter be effective. The method is formulated from the outset through the most general multi-reference, i.e. beyond mean-field, implementation such that the single-reference, i.e. "mean-field", derives as a particular case. As such, a key point of the presentation provided here is to demonstrate that the multi-reference EDF method can indeed be formulated in a mathematically meaningful fashion even if E[g',g] does not derive from a genuine Hamilton operator. In particular, the restoration of symmetries can be entirely formulated without making any reference to a projected state, i.e. within a genuine EDF framework. However, and as is illustrated in the present document, a mathematically meaningful formulation does not guarantee that the formalism is sound from a physical standpoint. The price at which the latter can be enforced as well in the future is eventually alluded to.
A half century of density functional theory
Zangwill, Andrew
2015-07-15
Today’s most popular method for calculating the electronic structure of atoms, molecules, liquids, solids, and plasmas began as a bold hypothesis: The electron density distribution completely characterizes the ground state of a many-electron system.
Ions in solution: Density corrected density functional theory (DC-DFT)
Kim, Min-Cheol; Sim, Eunji; Burke, Kieron
2014-05-14
Standard density functional approximations often give questionable results for odd-electron radical complexes, with the error typically attributed to self-interaction. In density corrected density functional theory (DC-DFT), certain classes of density functional theory calculations are significantly improved by using densities more accurate than the self-consistent densities. We discuss how to identify such cases, and how DC-DFT applies more generally. To illustrate, we calculate potential energy surfaces of HO·Cl{sup −} and HO·H{sub 2}O complexes using various common approximate functionals, with and without this density correction. Commonly used approximations yield wrongly shaped surfaces and/or incorrect minima when calculated self consistently, while yielding almost identical shapes and minima when density corrected. This improvement is retained even in the presence of implicit solvent.
Optimizing a parametrized Thomas-Fermi-Dirac-Weizsäcker density functional for atoms.
Espinosa Leal, L A; Karpenko, A; Caro, M A; Lopez-Acevedo, O
2015-12-21
Because of issues with accuracy and transferability of existing orbital-free (OF) density functionals, OF functional development remains an active research area. However, due to numerical difficulties, all-electron self-consistent assessment of OF functionals is limited. Using an all-electron radial OFDFT code, we evaluate the performance of a parametrized OF functional for a wide range in parameter space. Specifically, we combine the parametrized Thomas-Fermi-Weizsäcker kinetic model (λ and γ for the fractions of Weizsäcker and Thomas-Fermi functionals, respectively) with a local density approximation (LDA) for the exchange-correlation functional. In order to obtain the converged results for λ values other than λ = 1, we use the potential scaling introduced in previous work. Because we work within a wide region in parameter space, this strategy provides an effective route towards better understanding of the parameter interplay that allows us to achieve good agreement with the Kohn-Sham (KS) model. Here, our interest lies in total energy, Euler equation eigenvalue, and electronic densities when the parameters are varied between 0.2 and 1.5. We observe that a one-to-one relation between λ and γ defines a region in parameter space that allows the atomic energies to be approximated with a very small average error (less than 3% percent for all the atoms studied) with respect to the KS reference energies. For each atom, the reference KS HOMO eigenvalue can also be reproduced with a similar error, but the one-to-one correspondence between λ and γ belongs to a different region of the same parameter space. Contrary to both properties, the atomic density behaves more smoothly and the error in reproducing the KS reference densities appears more insensitive to variation of the parameters (with mostly an average integrated difference of 0.15-0.20 |e| per electron). These results pave the way towards testing of parameter transferability and further systematic
a Renormalization Group Calculation of the Velocity - and Density-Density Correlation Functions.
NASA Astrophysics Data System (ADS)
Cowan, Mark Timothy
The velocity-velocity correlation function of a free field theory is obtained. The renormalization group, along with a 4-varepsilon expansion, is then used to find the leading order behavior of the velocity-velocity correlation function for an interacting field theory in the high temperature phase near the critical point. The details of the calculation of the density-density correlation function for Hedgehogs, in the context of a free field theory, is presented next. Finally the renormalization group, along with a 4-varepsilon expansion, is used to find the leading order behavior of the density-density correlation function for Hedgehogs in an interacting field theory near the critical point.
Fermionic density functional at a Feshbach resonance
Seidl, Michael; Bhaduri, Rajat K.
2007-05-15
We consider a dilute gas of neutral unpolarized fermionic atoms at zero temperature. The atoms interact via a short-range (tunable) attractive interaction. We demonstrate analytically a curious property of the gas at unitarity. Namely, the correlation energy of the gas, evaluated by second-order perturbation theory, has the same density dependence as the first-order exchange energy, and the two almost exactly cancel each other at a Feshbach resonance irrespective of the shape of the potential, provided ({mu}r{sub s})>>1. Here ({mu}){sup -1} is the range of the two-body potential, and r{sub s} is defined through the number density, n=3/(4{pi}r{sub s}{sup 3}). The implications of this result for universality are discussed.
Density functional theory for Yukawa fluids
NASA Astrophysics Data System (ADS)
Hatlo, Marius M.; Banerjee, Priyanka; Forsman, Jan; Lue, Leo
2012-08-01
We develop an approximate field theory for particles interacting with a generalized Yukawa potential. This theory improves and extends a previous splitting field theory, originally developed for counterions around a fixed charge distribution. The resulting theory bridges between the second virial approximation, which is accurate at low particle densities, and the mean-field approximation, accurate at high densities. We apply this theory to charged, screened ions in bulk solution, modeled to interact with a Yukawa potential; the theory is able to accurately reproduce the thermodynamic properties of the system over a broad range of conditions. The theory is also applied to "dressed counterions," interacting with a screened electrostatic potential, contained between charged plates. It is found to work well from the weak coupling to the strong coupling limits. The theory is able to reproduce the counterion profiles and force curves for closed and open systems obtained from Monte Carlo simulations.
Density-functional Monte-Carlo simulation of CuZn order-disorder transition
Khan, Suffian N.; Eisenbach, Markus
2016-01-25
We perform a Wang-Landau Monte Carlo simulation of a Cu0.5Zn0.5 order-disorder transition using 250 atoms and pairwise atom swaps inside a 5 x 5 x 5 BCC supercell. Each time step uses energies calculated from density functional theory (DFT) via the all-electron Korringa-Kohn- Rostoker method and self-consistent potentials. Here we find CuZn undergoes a transition from a disordered A2 to an ordered B2 structure, as observed in experiment. Our calculated transition temperature is near 870 K, comparing favorably to the known experimental peak at 750 K. We also plot the entropy, temperature, specific-heat, and short-range order as a function ofmore » internal energy.« less
Label-free all-electronic biosensing in microfluidic systems
NASA Astrophysics Data System (ADS)
Stanton, Michael A.
Label-free, all-electronic detection techniques offer great promise for advancements in medical and biological analysis. Electrical sensing can be used to measure both interfacial and bulk impedance changes in conducting solutions. Electronic sensors produced using standard microfabrication processes are easily integrated into microfluidic systems. Combined with the sensitivity of radiofrequency electrical measurements, this approach offers significant advantages over competing biological sensing methods. Scalable fabrication methods also provide a means of bypassing the prohibitive costs and infrastructure associated with current technologies. We describe the design, development and use of a radiofrequency reflectometer integrated into a microfluidic system towards the specific detection of biologically relevant materials. We developed a detection protocol based on impedimetric changes caused by the binding of antibody/antigen pairs to the sensing region. Here we report the surface chemistry that forms the necessary capture mechanism. Gold-thiol binding was utilized to create an ordered alkane monolayer on the sensor surface. Exposed functional groups target the N-terminus, affixing a protein to the monolayer. The general applicability of this method lends itself to a wide variety of proteins. To demonstrate specificity, commercially available mouse anti- Streptococcus Pneumoniae monoclonal antibody was used to target the full-length recombinant pneumococcal surface protein A, type 2 strain D39 expressed by Streptococcus Pneumoniae. We demonstrate the RF response of the sensor to both the presence of the surface decoration and bound SPn cells in a 1x phosphate buffered saline solution. The combined microfluidic sensor represents a powerful platform for the analysis and detection of cells and biomolecules.
Molecular dynamics simulation of liquid water: Hybrid density functionals
Todorova, T; Seitsonen, A; Hutter, J; Kuo, W; Mundy, C
2005-09-12
The structure, dynamical and electronic properties of liquid water utilizing different hybrid density functionals were tested within the plane wave framework of first principles molecular dynamics simulations. The computational approach, which employs modified functionals with short-ranged Hartree-Fock exchange, was first tested in calculations of the structural and bonding properties of the water dimer and cyclic water trimer. Liquid water simulations were performed at the state point of 350 K at the experimental density. Simulations included three different hybrid functionals, a meta functional, four gradient corrected functionals, the local density and Hartree-Fock approximation. It is found that hybrid functionals are superior in reproducing the experimental structure and dynamical properties as measured by the radial distribution function and self diffusion constant when compared to the pure density functionals. The local density and Hartree-Fock approximations show strongly over- and under-structured liquids, respectively. Hydrogen bond analysis shows that the hybrid functionals give slightly smaller averaged numbers of hydrogen bonds and similar hydrogen bond populations as pure density functionals. The average molecular dipole moments in the liquid from the three hybrid functionals are lower than from the corresponding pure density functionals.
Phonons in nonlocal van der Waals density functional theory
NASA Astrophysics Data System (ADS)
Sabatini, Riccardo; Küçükbenli, Emine; Pham, Cong Huy; de Gironcoli, Stefano
2016-06-01
We extend the formulation of density functional perturbation theory to treat nonlocal density functionals, accounting for van der Waals interactions, in a rigorous and efficient way. We provide a general formalism, suitable for any functional in this family, and give specific equations for the most widely used ones. We then study the lattice dynamics of graphite, comparing several nonlocal functionals and the local density approximation, showing that our recent revision of the VV10 functional [R. Sabatini et al., Phys. Rev. B 87, 041108(R) (2013), 10.1103/PhysRevB.87.041108] gives the best comparison with experiments.
Exact conditions on the temperature dependence of density functionals
NASA Astrophysics Data System (ADS)
Burke, K.; Smith, J. C.; Grabowski, P. E.; Pribram-Jones, A.
2016-05-01
Universal exact conditions guided the construction of most ground-state density functional approximations in use today. We derive the relation between the entropy and Mermin free energy density functionals for thermal density functional theory. Both the entropy and sum of kinetic and electron-electron repulsion functionals are shown to be monotonically increasing with temperature, while the Mermin functional is concave downwards. Analogous relations are found for both exchange and correlation. The importance of these conditions is illustrated in two extremes: the Hubbard dimer and the uniform gas.
Density-potential mapping in time-dependent density-functional theory
Maitra, N. T.; Todorov, T. N.; Woodward, C.; Burke, K.
2010-04-15
The key questions of uniqueness and existence in time-dependent density-functional theory are usually formulated only for potentials and densities that are analytic in time. Simple examples, standard in quantum mechanics, lead, however, to nonanalyticities. We reformulate these questions in terms of a nonlinear Schroedinger equation with a potential that depends nonlocally on the wave function.
Spin constraints on nuclear energy density functionals
NASA Astrophysics Data System (ADS)
Robledo, L. M.; Bernard, R. N.; Bertsch, G. F.
2014-02-01
The Gallagher-Moszkowski rule in the spectroscopy of odd-odd nuclei imposes a new spin constraint on the energy functionals for self-consistent mean field theory. The commonly used parametrization of the effective three-body interaction in the Gogny and Skyrme families of energy functionals is ill suited to satisfy the spin constraint. In particular, the Gogny parametrization of the three-body interaction has the spin dependence opposite to that required by the observed spectra. The two-body part has a correct sign, but in combination the rule is violated as often as not. We conclude that a new functional form is needed for the effective three-body interaction that can take into better account the different spin-isospin channels of the interaction.
Introduction to Classical Density Functional Theory by a Computational Experiment
ERIC Educational Resources Information Center
Jeanmairet, Guillaume; Levy, Nicolas; Levesque, Maximilien; Borgis, Daniel
2014-01-01
We propose an in silico experiment to introduce the classical density functional theory (cDFT). Density functional theories, whether quantum or classical, rely on abstract concepts that are nonintuitive; however, they are at the heart of powerful tools and active fields of research in both physics and chemistry. They led to the 1998 Nobel Prize in…
Nuclear collective excitations: A relativistic density functional approach
NASA Astrophysics Data System (ADS)
Piekarewicz, J.
2015-08-01
Density functional theory provides the most promising, and likely unique, microscopic framework to describe nuclear systems ranging from finite nuclei to neutron stars. Properly optimized energy density functionals define a new paradigm in nuclear theory where predictive capability is possible and uncertainty quantification is demanded. Moreover, density functional theory offers a consistent approach to the linear response of the nuclear ground state. In this paper, we review the fundamental role played by nuclear collective modes in uncovering novel excitations and in guiding the optimization of the density functional. Indeed, without collective excitations the determination of the density functional remains incomplete. Without collective excitations, the equation of state of neutron-rich matter continues to be poorly constrained. We conclude with a discussion of some of the remaining challenges in this field and propose a path forward to address these challenges.
Petrenko, Taras; Kossmann, Simone; Neese, Frank
2011-02-01
In this paper, we present the implementation of efficient approximations to time-dependent density functional theory (TDDFT) within the Tamm-Dancoff approximation (TDA) for hybrid density functionals. For the calculation of the TDDFT/TDA excitation energies and analytical gradients, we combine the resolution of identity (RI-J) algorithm for the computation of the Coulomb terms and the recently introduced "chain of spheres exchange" (COSX) algorithm for the calculation of the exchange terms. It is shown that for extended basis sets, the RIJCOSX approximation leads to speedups of up to 2 orders of magnitude compared to traditional methods, as demonstrated for hydrocarbon chains. The accuracy of the adiabatic transition energies, excited state structures, and vibrational frequencies is assessed on a set of 27 excited states for 25 molecules with the configuration interaction singles and hybrid TDDFT/TDA methods using various basis sets. Compared to the canonical values, the typical error in transition energies is of the order of 0.01 eV. Similar to the ground-state results, excited state equilibrium geometries differ by less than 0.3 pm in the bond distances and 0.5° in the bond angles from the canonical values. The typical error in the calculated excited state normal coordinate displacements is of the order of 0.01, and relative error in the calculated excited state vibrational frequencies is less than 1%. The errors introduced by the RIJCOSX approximation are, thus, insignificant compared to the errors related to the approximate nature of the TDDFT methods and basis set truncation. For TDDFT/TDA energy and gradient calculations on Ag-TB2-helicate (156 atoms, 2732 basis functions), it is demonstrated that the COSX algorithm parallelizes almost perfectly (speedup ~26-29 for 30 processors). The exchange-correlation terms also parallelize well (speedup ~27-29 for 30 processors). The solution of the Z-vector equations shows a speedup of ~24 on 30 processors. The
NASA Astrophysics Data System (ADS)
Petrenko, Taras; Kossmann, Simone; Neese, Frank
2011-02-01
In this paper, we present the implementation of efficient approximations to time-dependent density functional theory (TDDFT) within the Tamm-Dancoff approximation (TDA) for hybrid density functionals. For the calculation of the TDDFT/TDA excitation energies and analytical gradients, we combine the resolution of identity (RI-J) algorithm for the computation of the Coulomb terms and the recently introduced "chain of spheres exchange" (COSX) algorithm for the calculation of the exchange terms. It is shown that for extended basis sets, the RIJCOSX approximation leads to speedups of up to 2 orders of magnitude compared to traditional methods, as demonstrated for hydrocarbon chains. The accuracy of the adiabatic transition energies, excited state structures, and vibrational frequencies is assessed on a set of 27 excited states for 25 molecules with the configuration interaction singles and hybrid TDDFT/TDA methods using various basis sets. Compared to the canonical values, the typical error in transition energies is of the order of 0.01 eV. Similar to the ground-state results, excited state equilibrium geometries differ by less than 0.3 pm in the bond distances and 0.5° in the bond angles from the canonical values. The typical error in the calculated excited state normal coordinate displacements is of the order of 0.01, and relative error in the calculated excited state vibrational frequencies is less than 1%. The errors introduced by the RIJCOSX approximation are, thus, insignificant compared to the errors related to the approximate nature of the TDDFT methods and basis set truncation. For TDDFT/TDA energy and gradient calculations on Ag-TB2-helicate (156 atoms, 2732 basis functions), it is demonstrated that the COSX algorithm parallelizes almost perfectly (speedup ˜26-29 for 30 processors). The exchange-correlation terms also parallelize well (speedup ˜27-29 for 30 processors). The solution of the Z-vector equations shows a speedup of ˜24 on 30 processors. The
NASA Astrophysics Data System (ADS)
Bochevarov, Arteum D.; Friesner, Richard A.
2008-01-01
We investigate one of the fundamental observables, electronic charge density, as produced by a number of popular functionals of the density functional theory (DFT): SVWN5, B3LYP, B3LYP, OLYP, O3LYP, BP86, B3P86, O3P86, and PBE using restricted and unrestricted orbitals. Measuring and comparing the quality of the densities could tell us more about the physical soundness of the functional models. The study is performed on the small molecules He, H2, LiH, H4 in an extensive range of correlation-consistent basis sets. We compare DFT densities to those of full configuration interaction (FCI) under the assumption that the FCI density in the largest employed basis set is sufficiently close to the exact one. For LiH and H4, we also compare the DFT densities to those of CCSD. The SVWN5 functional consistently shows the worst performance. The OPTX exchange functional regularly beats the Becke exchange. Among the best performers are all the hybrid functionals, the novel O3P86 being the most accurate in most cases. The popular functional B3LYP was consistently outmatched by O3LYP, and produced, in fact, some of the poorest densities among the hybrids. CCSD was found to produce much more accurate densities than any DFT functional in the case of LiH in equilibrium geometry, but was sometimes outperformed by DFT in the case of slightly stretched H4, where CCSD theory itself starts to break down. Surprisingly, as one stretches the H2 molecule, BP86 and PBE improve the description of density although such behavior is not observed in other systems. We conclude by reasoning how functionals such as B3LYP, despite being quite average for density, could still be very successful in predicting thermodynamic properties.
Molecular density functional theory of water including density-polarization coupling.
Jeanmairet, Guillaume; Levy, Nicolas; Levesque, Maximilien; Borgis, Daniel
2016-06-22
We present a three-dimensional molecular density functional theory of water derived from first-principles that relies on the particle's density and multipolar polarization density and includes the density-polarization coupling. This brings two main benefits: (i) scalar density and vectorial multipolar polarization density fields are much more tractable and give more physical insight than the full position and orientation densities, and (ii) it includes the full density-polarization coupling of water, that is known to be non-vanishing but has never been taken into account. Furthermore, the theory requires only the partial charge distribution of a water molecule and three measurable bulk properties, namely the structure factor and the Fourier components of the longitudinal and transverse dielectric susceptibilities. PMID:27116250
The benchmark of gutzwiller density functional theory in hydrogen systems
Yao, Y.; Wang, Cai-Zhuang; Ho, Kai-Ming
2012-02-23
We propose an approximate form of the exchange-correlation energy functional for the Gutzwiller density functional theory. It satisfies certain physical constraints in both weak and strong electron correlation limits. We benchmark the Gutzwiller density functional approximation in the hydrogen systems, where the static correlation error is shown to be negligible. The good transferability is demonstrated by applications to the hydrogen molecule and some crystal structures.
The Benchmark of Gutzwiller Density Functional Theory in Hydrogen Systems
Yao, Yongxin; Wang, Cai-Zhuang; Ho, Kai-Ming
2011-01-13
We propose an approximate form of the exchange-correlation energy functional for the Gutzwiller density functional theory. It satisfies certain physical constraints in both weak and strong electron correlation limits. We benchmark the Gutzwiller density functional approximation in the hydrogen systems, where the static correlation error is shown to be negligible. The good transferability is demonstrated by applications to the hydrogen molecule and some crystal structures. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012
Impact ionization in GaAs: A screened exchange density-functional approach
Picozzi, S.; Asahi, R.; Geller, C. B.; Continenza, A.; Freeman, A. J.
2001-08-13
Results are presented of a fully ab initio calculation of impact ionization rates in GaAs within the density functional theory framework, using a screened-exchange formalism and the highly precise all-electron full-potential linearized augmented plane wave method. The calculated impact ionization rates show a marked orientation dependence in k space, indicating the strong restrictions imposed by the conservation of energy and momentum. This anisotropy diminishes as the impacting electron energy increases. A Keldysh type fit performed on the energy-dependent rate shows a rather soft edge and a threshold energy greater than the direct band gap. The consistency with available Monte Carlo and empirical pseudopotential calculations shows the reliability of our approach and paves the way to ab initio calculations of pair production rates in new and more complex materials.
Generalized van der Waals density functional theory for nonuniform polymers
Patra, Chandra N.; Yethiraj, Arun
2000-01-15
A density functional theory is presented for the effect of attractions on the structure of polymers at surfaces. The theory treats the ideal gas functional exactly, and uses a weighted density approximation for the hard chain contribution to the excess free energy functional. The attractive interactions are treated using a van der Waals approximation. The theory is in good agreement with computer simulations for the density profiles at surfaces for a wide range of densities and temperatures, except for low polymer densities at low temperatures where it overestimates the depletion of chains from the surface. This deficiency is attributed to the neglect of liquid state correlations in the van der Waals term of the free energy functional. (c) 2000 American Institute of Physics.
Exact maps in density functional theory for lattice models
NASA Astrophysics Data System (ADS)
Dimitrov, Tanja; Appel, Heiko; Fuks, Johanna I.; Rubio, Angel
2016-08-01
In the present work, we employ exact diagonalization for model systems on a real-space lattice to explicitly construct the exact density-to-potential and graphically illustrate the complete exact density-to-wavefunction map that underly the Hohenberg–Kohn theorem in density functional theory. Having the explicit wavefunction-to-density map at hand, we are able to construct arbitrary observables as functionals of the ground-state density. We analyze the density-to-potential map as the distance between the fragments of a system increases and the correlation in the system grows. We observe a feature that gradually develops in the density-to-potential map as well as in the density-to-wavefunction map. This feature is inherited by arbitrary expectation values as functional of the ground-state density. We explicitly show the excited-state energies, the excited-state densities, and the correlation entropy as functionals of the ground-state density. All of them show this exact feature that sharpens as the coupling of the fragments decreases and the correlation grows. We denominate this feature as intra-system steepening and discuss how it relates to the well-known inter-system derivative discontinuity. The inter-system derivative discontinuity is an exact concept for coupled subsystems with degenerate ground state. However, the coupling between subsystems as in charge transfer processes can lift the degeneracy. An important conclusion is that for such systems with a near-degenerate ground state, the corresponding cut along the particle number N of the exact density functionals is differentiable with a well-defined gradient near integer particle number.
NASA Astrophysics Data System (ADS)
Painter, G. S.; Averill, F. W.
1983-11-01
The principle of augmentation, used to introduce inner-atom core structure into slowly varying basis functions, is applied to Gaussian orbitals to define a new basis set for highly accurate total-energy calculations for atomic clusters within the density-functional formalism. Diffuse Gaussian-orbital tails are matched continuously and differentiably to inner-atom numeric radial functions at the atomic-sphere radius. Major advantages of Gaussian-orbital basis sets are acquired without the need for numerous Gaussians of large exponent for the core region. The numeric functions used inside the atom permit essentially exact solutions for that region. Procedures are described which recover use of the efficient integral algorithms for the Gaussian-orbital-tail matrix elements. The interactions over the structured inner-atom region are treated by efficient integrand smoothing and integration procedures for the sphere. The new augmented Gaussian basis removes the primary limitations on the use of Gaussian orbitals for heavy atoms. As an illustration the method is applied to the copper dimer in an all-electron framework within the local-spin-density approximation (LSDA). The calculated binding energy, equilibrium separation, and first ionization potential of Cu2 are within 2% of experiment within the Xα model. Excitation energies are better described within more recent refined exchange-correlation functionals. These all-electron results show the LSDA model predicts a slightly contracted bond length for Cu2, consistent with bulk LSDA calculations for the 3d transition-metal series.
Postfragmentation density function for bacterial aggregates in laminar flow
NASA Astrophysics Data System (ADS)
Byrne, Erin; Bortz, David M.; Dzul, Steve; Solomon, Michael; Younger, John
2011-04-01
The postfragmentation probability density of daughter flocs is one of the least well-understood aspects of modeling flocculation. We use three-dimensional positional data of Klebsiella pneumoniae bacterial flocs in suspension and the knowledge of hydrodynamic properties of a laminar flow field to construct a probability density function of floc volumes after a fragmentation event. We provide computational results which predict that the primary fragmentation mechanism for large flocs is erosion. The postfragmentation probability density function has a strong dependence on the size of the original floc and indicates that most fragmentation events result in clumps of one to three bacteria eroding from the original floc. We also provide numerical evidence that exhaustive fragmentation yields a limiting density inconsistent with the log-normal density predicted in the literature, most likely due to the heterogeneous nature of K. pneumoniae flocs. To support our conclusions, artificial flocs were generated and display similar postfragmentation density and exhaustive fragmentation.
Predicting Pt-195 NMR chemical shift using new relativistic all-electron basis set.
Paschoal, D; Guerra, C Fonseca; de Oliveira, M A L; Ramalho, T C; Dos Santos, H F
2016-10-01
Predicting NMR properties is a valuable tool to assist the experimentalists in the characterization of molecular structure. For heavy metals, such as Pt-195, only a few computational protocols are available. In the present contribution, all-electron Gaussian basis sets, suitable to calculate the Pt-195 NMR chemical shift, are presented for Pt and all elements commonly found as Pt-ligands. The new basis sets identified as NMR-DKH were partially contracted as a triple-zeta doubly polarized scheme with all coefficients obtained from a Douglas-Kroll-Hess (DKH) second-order scalar relativistic calculation. The Pt-195 chemical shift was predicted through empirical models fitted to reproduce experimental data for a set of 183 Pt(II) complexes which NMR sign ranges from -1000 to -6000 ppm. Furthermore, the models were validated using a new set of 75 Pt(II) complexes, not included in the descriptive set. The models were constructed using non-relativistic Hamiltonian at density functional theory (DFT-PBEPBE) level with NMR-DKH basis set for all atoms. For the best model, the mean absolute deviation (MAD) and the mean relative deviation (MRD) were 150 ppm and 6%, respectively, for the validation set (75 Pt-complexes) and 168 ppm (MAD) and 5% (MRD) for all 258 Pt(II) complexes. These results were comparable with relativistic DFT calculation, 200 ppm (MAD) and 6% (MRD). © 2016 Wiley Periodicals, Inc. PMID:27510431
Integration, Continuity and a Connection with Probability Density Functions
ERIC Educational Resources Information Center
Samuels, M.
2006-01-01
This note considers functions of two variables which are continuous on a possibly unbounded closed region in [vertical bar]R[squared], and the functions of one variable obtained by integrating out the other variable over this region. The question of continuity of these functions is investigated, as are connections with joint density and marginal…
NASA Astrophysics Data System (ADS)
Knuth, Franz; Carbogno, Christian; Atalla, Viktor; Blum, Volker; Scheffler, Matthias
2015-05-01
We derive and implement the strain derivatives of the total energy of solids, i.e., the analytic stress tensor components, in an all-electron, numeric atom-centered orbital based density-functional formalism. We account for contributions that arise in the semi-local approximation (LDA/GGA) as well as in the generalized Kohn-Sham case, in which a fraction of exact exchange (hybrid functionals) is included. In this work, we discuss the details of the implementation including the numerical corrections for sparse integrations grids which allow to produce accurate results. We validate the implementation for a variety of test cases by comparing to strain derivatives performed via finite differences. Additionally, we include the detailed definition of the overlapping atom-centered integration formalism used in this work to obtain total energies and their derivatives.
Optical properties of alkali halide crystals from all-electron hybrid TD-DFT calculations
Webster, R. Harrison, N. M.; Bernasconi, L.
2015-06-07
We present a study of the electronic and optical properties of a series of alkali halide crystals AX, with A = Li, Na, K, Rb and X = F, Cl, Br based on a recent implementation of hybrid-exchange time-dependent density functional theory (TD-DFT) (TD-B3LYP) in the all-electron Gaussian basis set code CRYSTAL. We examine, in particular, the impact of basis set size and quality on the prediction of the optical gap and exciton binding energy. The formation of bound excitons by photoexcitation is observed in all the studied systems and this is shown to be correlated to specific features of the Hartree-Fock exchange component of the TD-DFT response kernel. All computed optical gaps and exciton binding energies are however markedly below estimated experimental and, where available, 2-particle Green’s function (GW-Bethe-Salpeter equation, GW-BSE) values. We attribute this reduced exciton binding to the incorrect asymptotics of the B3LYP exchange correlation ground state functional and of the TD-B3LYP response kernel, which lead to a large underestimation of the Coulomb interaction between the excited electron and hole wavefunctions. Considering LiF as an example, we correlate the asymptotic behaviour of the TD-B3LYP kernel to the fraction of Fock exchange admixed in the ground state functional c{sub HF} and show that there exists one value of c{sub HF} (∼0.32) that reproduces at least semi-quantitatively the optical gap of this material.
Testing for parity violation in nuclei using spin density matrices for nuclear density functionals
NASA Astrophysics Data System (ADS)
Barrett, B. R.; Giraud, B. G.
2015-06-01
The spin density matrix (SDM) used in atomic and molecular physics is revisited for nuclear physics, in the context of the radial density functional theory. The vector part of the SDM defines a ‘hedgehog’ situation, which exists only if nuclear states contain some amount of parity violation. A toy model is given as an illustrative example.
Fluctuation-dissipation theorem density-functional theory
NASA Astrophysics Data System (ADS)
Furche, Filipp; Van Voorhis, Troy
2005-04-01
Using the fluctuation-dissipation theorem (FDT) in the context of density-functional theory (DFT), one can derive an exact expression for the ground-state correlation energy in terms of the frequency-dependent density response function. When combined with time-dependent density-functional theory, a new class of density functionals results that use approximations to the exchange-correlation kernel fxc as input. This FDT-DFT scheme holds promise to solve two of the most distressing problems of conventional Kohn-Sham DFT: (i) It leads to correlation energy functionals compatible with exact exchange, and (ii) it naturally includes dispersion. The price is a moderately expensive O(N6) scaling of computational cost and a slower basis set convergence. These general features of FDT-DFT have all been recognized previously. In this paper, we present the first benchmark results for a set of molecules using FDT-DFT beyond the random-phase approximation (RPA)—that is, the first such results with fxc≠0. We show that kernels derived from the adiabatic local-density approximation and other semilocal functionals suffer from an "ultraviolet catastrophe," producing a pair density that diverges at small interparticle distance. Nevertheless, dispersion interactions can be treated accurately if hybrid functionals are employed, as is demonstrated for He2 and HeNe. We outline constraints that future approximations to fxc should satisfy and discuss the prospects of FDT-DFT.
Charge and spin fluctuations in the density functional theory
Gyoerffy, B.L.; Barbieri, A. . H.H. Wills Physics Lab.); Staunton, J.B. . Dept. of Physics); Shelton, W.A.; Stocks, G.M. )
1990-01-01
We introduce a conceptual framework which allow us to treat charge and spin fluctuations about the Local density Approximation (LDA) to the Density Functional Theory (DFT). We illustrate the approach by explicit study of the Disordered Local Moment (DLM) state in Fe above the Curie Temperature {Tc} and the Mott insulating state in MnO. 27 refs., 6 figs.
Density Functional Model for Nondynamic and Strong Correlation.
Kong, Jing; Proynov, Emil
2016-01-12
A single-term density functional model for the left-right nondynamic/strong electron correlation is presented based on single-determinant Kohn-Sham density functional theory. It is derived from modeling the adiabatic connection for kinetic correlation energy based on physical arguments, with the correlation potential energy based on the Becke'13 model ( Becke, A.D. J. Chem. Phys . 2013 , 138 , 074109 ). This functional satisfies some known scaling relationships for correlation functionals. The fractional spin error is further reduced substantially with a new density-functional correction. Preliminary tests with self-consistent-field implementation show that the model, with only three empirical parameters, recovers the majority of left-right nondynamic/strong correlation upon bond dissociation and performs reasonably well for atomization energies and singlet-triplet energy splittings. This study also demonstrates the feasibility of developing DFT functionals for nondynamic and strong correlation within the single-determinant KS scheme. PMID:26636190
Density and Spin Response Functions in Ultracold Fermionic Atom Gases
Mihaila, Bogdan; Blagoev, Krastan B.; Balatsky, Alexander V.; Smith, Darryl L.; Gaudio, Sergio; Littlewood, Peter B.
2005-08-26
We propose a new method of detecting the onset of superfluidity in a two-component ultracold fermionic gas of atoms governed by an attractive short-range interaction. By studying the two-body correlation functions we find that a measurement of the momentum distribution of the density and spin-response functions allows one to access separately the normal and anomalous densities. The change in sign at low momentum transfer of the normal-ordered part of the density response function signals the transition between a BEC and a BCS regime, characterized by small and large pairs, respectively. This change in sign of the density response function represents an unambiguous signature of the BEC-to-BCS crossover. Spin rotational symmetry breaking due to the magnetic field, if observed, can be used to validate the one-channel model.
Density Functional Theory with Dissipation: Transport through Single Molecules
Kieron Burke
2012-04-30
A huge amount of fundamental research was performed on this grant. Most of it focussed on fundamental issues of electronic structure calculations of transport through single molecules, using density functional theory. Achievements were: (1) First density functional theory with dissipation; (2) Pseudopotential plane wave calculations with master equation; (3) Weak bias limit; (4) Long-chain conductance; and (5) Self-interaction effects in tunneling.
Gutzwiller density functional theory for correlated electron systems
Ho, K. M.; Schmalian, J.; Wang, C. Z.
2008-02-04
We develop a density functional theory (DFT) and formalism for correlated electron systems by taking as reference an interacting electron system that has a ground state wave function which exactly obeys the Gutzwiller approximation for all one-particle operators. The solution of the many-electron problem is mapped onto the self-consistent solution of a set of single-particle Schroedinger equations, analogously to standard DFT-local density approximation calculations.
Preface: Special Topic on Advances in Density Functional Theory
Yang, Weitao
2014-05-14
This Special Topic Issue on the Advances in Density Functional Theory, published as a celebration of the fifty years of density functional theory, contains a retrospective article, a perspective article, and a collection of original research articles that showcase recent theoretical advances in the field. It provides a timely discussion reflecting a cross section of our understanding, and the theoretical and computational developments, which have significant implications in broad areas of sciences and engineering.
Preface: Special topic on advances in density functional theory.
Yang, Weitao
2014-05-14
This Special Topic Issue on the Advances in Density Functional Theory, published as a celebration of the fifty years of density functional theory, contains a retrospective article, a perspective article, and a collection of original research articles that showcase recent theoretical advances in the field. It provides a timely discussion reflecting a cross section of our understanding, and the theoretical and computational developments, which have significant implications in broad areas of sciences and engineering. PMID:24832306
Reflection-Asymmetric Nuclear Deformations within the Density Functional Theory
Olsen, E; Erler, J; Nazarewicz, W.; Stoitsov, M
2012-01-01
Within the nuclear density functional theory (DFT) we study the effect of reflection- asymmetric shapes on ground-state binding energies and binding energy differences. To this end, we developed the new DFT solver axialhfb that uses an approximate second-order gradient to solve the Hartree-Fock-Bogoliubov equations of superconducting DFT with the quasi-local Skyrme energy density functionals. Illustrative calculations are carried out for even- even isotopes of radium and thorium.
Density functional calculations for prediction of ultra-thin film structure and properties
Trickey, S.B.; Boettger, J.C.
1995-09-01
Most of the published theoretical and calculational effort on unsupported, ordered, ultra-thin films (``UTF``) in vacuo has focused on the thickest computationally feasible systems as models for surface properties of semi-infinite slabs. Crystalline periodic length scales in two cartesian dimensions combined with molecular- scale thickness in the third, however, make UTF`s strong candidates for the occurrence of quantum interference effects. Many UTF properties were predicted first from jellium slab models. A noteworthy prediction was that there would be large oscillations in the work function as a function of layer number. Extensive calculations on a variety of N-layers (N = 1,2,3... atomic planes) using all-electron, full-potential, local-spin-density approximation techniques show that the work function oscillation is weaker than expected but that there are significant layer-number dependences in the equilibrium lattice parameters, inter-planar spacings, electronic structure, density of states, and electronic stopping power. This paper reviews our own calculations as well as some others. Our objectives include the discernment of systematics within UTF`s, systematics in relationship to their counterpart crystals, relationship with surface properties, and appraisal of challenges to current models and methods.
Energy Densities in the Strong-Interaction Limit of Density Functional Theory.
Mirtschink, André; Seidl, Michael; Gori-Giorgi, Paola
2012-09-11
We discuss energy densities in the strong-interaction limit of density functional theory, deriving an exact expression within the definition (gauge) of the electrostatic potential of the exchange-correlation hole. Exact results for small atoms and small model quantum dots (Hooke's atoms) are compared with available approximations defined in the same gauge. The idea of a local interpolation along the adiabatic connection is discussed, comparing the energy densities of the Kohn-Sham, the physical, and the strong-interacting systems. We also use our results to analyze the local version of the Lieb-Oxford bound, widely used in the construction of approximate exchange-correlation functionals. PMID:26605721
Comments on the locality in density-functional theory
Lindgren, Ingvar; Salomonson, Sten
2003-05-01
The 'locality hypothesis' in density-functional theory (DFT), implying that the functional derivative is equivalent to a multiplicative local function, forms the basis of models of Kohn-Sham type. This has been generally accepted by the community since the advent of the model, and has later been formally proved for a large class of functionals. The hypothesis has recently been questioned by Nesbet [Phys. Rev. A 58, R12 (1998) and Phys. Rev. A 65, 010502 (2001)], who claims that it fails for the kinetic-energy functional for a system with more than two noninteracting electrons with a nondegenerate ground state. This conclusion has been questioned by Gal [Phys. Rev. A 62, 044501 (2000)] and by Holas and March [Phys. Rev. A 64, 016501 (2001)]. We claim that the arguments of Nesbet are incorrect, since the orbital functional used for the kinetic energy is not a unique functional of the total density in the domain of unnormalized orbitals. We have demonstrated that with a proper definition of the kinetic energy, which is a unique density functional also in the unnormalized region, the derivative can be represented by a single local multiplicative function for all v-representable densities. Therefore, we consider the controversy connected with the issue raised by Nesbet as resolved. We believe that the proof of the differentiability given here can be extended to larger groups of DFT functionals, and works along these lines are in progress.
Density functional theory for polymeric systems in 2D
NASA Astrophysics Data System (ADS)
Słyk, Edyta; Roth, Roland; Bryk, Paweł
2016-06-01
We propose density functional theory for polymeric fluids in two dimensions. The approach is based on Wertheim’s first order thermodynamic perturbation theory (TPT) and closely follows density functional theory for polymers proposed by Yu and Wu (2002 J. Chem. Phys. 117 2368). As a simple application we evaluate the density profiles of tangent hard-disk polymers at hard walls. The theoretical predictions are compared against the results of the Monte Carlo simulations. We find that for short chain lengths the theoretical density profiles are in an excellent agreement with the Monte Carlo data. The agreement is less satisfactory for longer chains. The performance of the theory can be improved by recasting the approach using the self-consistent field theory formalism. When the self-avoiding chain statistics is used, the theory yields a marked improvement in the low density limit. Further improvements for long chains could be reached by going beyond the first order of TPT.
Density functional theory for polymeric systems in 2D.
Słyk, Edyta; Roth, Roland; Bryk, Paweł
2016-06-22
We propose density functional theory for polymeric fluids in two dimensions. The approach is based on Wertheim's first order thermodynamic perturbation theory (TPT) and closely follows density functional theory for polymers proposed by Yu and Wu (2002 J. Chem. Phys. 117 2368). As a simple application we evaluate the density profiles of tangent hard-disk polymers at hard walls. The theoretical predictions are compared against the results of the Monte Carlo simulations. We find that for short chain lengths the theoretical density profiles are in an excellent agreement with the Monte Carlo data. The agreement is less satisfactory for longer chains. The performance of the theory can be improved by recasting the approach using the self-consistent field theory formalism. When the self-avoiding chain statistics is used, the theory yields a marked improvement in the low density limit. Further improvements for long chains could be reached by going beyond the first order of TPT. PMID:27115343
Franca, Vivian V.; D'Amico, Irene
2011-04-15
We derive an analytical density functional for the single-site entanglement of the one-dimensional homogeneous Hubbard model by means of an approximation to the linear entropy. We show that this very simple density functional reproduces quantitatively the exact results. We then use this functional as input for a local-density approximation to the single-site entanglement of inhomogeneous systems. We illustrate the power of this approach in a harmonically confined system, which could simulate recent experiments with ultracold atoms in optical lattices as well as in a superlattice and in an impurity system. The impressive quantitative agreement with numerical calculations--which includes reproducing subtle signatures of the particle density stages--shows that our density functional can provide entanglement calculations for actual experiments via density measurements. Next we use our functional to calculate the entanglement in disordered systems. We find that, in contrast with the expectation that disorder destroys the entanglement, there exist regimes for which the entanglement remains almost unaffected by the presence of disordered impurities.
Reactivity of Graphene Investigated by Density-Functional Theory
NASA Astrophysics Data System (ADS)
Soni, Himadri; Gebhardt, Julian; Görling, Andreas; Chair of Theoretical Chemistry Team
Using spin-polarized density-functional theory, we study the adsorption and reaction of hydrogen and fluorine with graphene. Graphene has a bipartite lattice with two different sublattices and hence, due to Lieb's theorem, the inequality between two sublattices should lead to a net magnetic moment upon adsorption of hydrogen or fluorine. Our calculations using density-functional theory with the generalized gradient approximation predict a magnetic moment of 1 µB for a single hydrogen adsorbed on graphene but not for a single fluorine atom adsorbed on graphene. Switching to hybrid density-functional theory with the HSE functional, we obtain a magnetic moment of 1 µB for of a single fluorine atom adsorption on graphene. This is in line with work of Kim et al., who also found in density-functional theory calculations with the HSE exchange-correlation functional spin-polarization for a fluorine adatom on graphene. Here, we present a systematic study of the reactivity and relevant adsorption mechanism for single-sided graphene, i.e., a graphene sheet which is accessible by an adsorbate from only one side with hydrogen and fluorine using hybrid density-functional theory. German Research Council (DFG) by the Collaborative Research Center 953.
Range Separation and Local Hybridization in Density Functional Theory†
Henderson, Thomas M.; Janesko, Benjamin G.; Scuseria, Gustavo E.
2016-01-01
Kohn–Sham density functional theory has become a standard method for modeling energetic, spectroscopic, and chemical reactivity properties of large molecules and solids. Density functional theory provides a rigorous theoretical framework for modeling the many-body exchange-correlation effects that dominate the computational cost of traditional wave function approaches. The advent of hybrid exchange-correlation functionals which incorporate a fraction of nonlocal exact exchange has solidified the prominence of density functional theory within computational chemistry. Hybrids provide accurate treatments of properties such as thermochemistry and molecular geometry. But they also exhibit some rather spectacular failures, and often contain multiple empirical parameters. This article reviews our work on developing novel exchange-correlation functionals that build upon the successes of global hybrids. We focus on more flexible functional forms, including local and range-separated hybrid functionals, constructed to obey known exact constraints and (ideally) to incorporate a minimum of empirical parametrization. The article places our work within the context of some other new approximate density functionals and discusses prospects for future work. PMID:19006280
Optimal-transport formulation of electronic density-functional theory
NASA Astrophysics Data System (ADS)
Buttazzo, Giuseppe; De Pascale, Luigi; Gori-Giorgi, Paola
2012-06-01
The most challenging scenario for Kohn-Sham density-functional theory, that is, when the electrons move relatively slowly trying to avoid each other as much as possible because of their repulsion (strong-interaction limit), is reformulated here as an optimal transport (or mass transportation theory) problem, a well-established field of mathematics and economics. In practice, we show that to solve the problem of finding the minimum possible internal repulsion energy for N electrons in a given density ρ(r) is equivalent to find the optimal way of transporting N-1 times the density ρ into itself, with the cost function given by the Coulomb repulsion. We use this link to set the strong-interaction limit of density-functional theory on firm ground and to discuss the potential practical aspects of this reformulation.
Relaxation of Actinide Surfaces: An All Electron Study
NASA Astrophysics Data System (ADS)
Atta-Fynn, Raymond; Dholabhai, Pratik; Ray, Asok
2006-10-01
Fully relativistic full potential density functional calculations with a linearized augmented plane wave plus local orbitals basis (LAPW + lo) have been performed to investigate the relaxations of heavy actinide surfaces, namely the (111) surface of fcc δ-Pu and the (0001) surface of dhcp Am using WIEN2k. This code uses the LAPW + lo method with the unit cell divided into non-overlapping atom-centered spheres and an interstitial region. The APW+lo basis is used to describe all s, p, d, and f states and LAPW basis to describe all higher angular momentum states. Each surface was modeled by a three-layer periodic slab separated by 60 Bohr vacuum with four atoms per surface unit cell. In general, we have found a contraction of the interlayer separations for both Pu and Am. We will report, in detail, the electronic and geometric structures of the relaxed surfaces and comparisons with the respective non-relaxed surfaces.
Optimization of an exchange-correlation density functional for water.
Fritz, Michelle; Fernández-Serra, Marivi; Soler, José M
2016-06-14
We describe a method, that we call data projection onto parameter space (DPPS), to optimize an energy functional of the electron density, so that it reproduces a dataset of experimental magnitudes. Our scheme, based on Bayes theorem, constrains the optimized functional not to depart unphysically from existing ab initio functionals. The resulting functional maximizes the probability of being the "correct" parameterization of a given functional form, in the sense of Bayes theory. The application of DPPS to water sheds new light on why density functional theory has performed rather poorly for liquid water, on what improvements are needed, and on the intrinsic limitations of the generalized gradient approximation to electron exchange and correlation. Finally, we present tests of our water-optimized functional, that we call vdW-DF-w, showing that it performs very well for a variety of condensed water systems. PMID:27305990
Optimization of an exchange-correlation density functional for water
NASA Astrophysics Data System (ADS)
Fritz, Michelle; Fernández-Serra, Marivi; Soler, José M.
2016-06-01
We describe a method, that we call data projection onto parameter space (DPPS), to optimize an energy functional of the electron density, so that it reproduces a dataset of experimental magnitudes. Our scheme, based on Bayes theorem, constrains the optimized functional not to depart unphysically from existing ab initio functionals. The resulting functional maximizes the probability of being the "correct" parameterization of a given functional form, in the sense of Bayes theory. The application of DPPS to water sheds new light on why density functional theory has performed rather poorly for liquid water, on what improvements are needed, and on the intrinsic limitations of the generalized gradient approximation to electron exchange and correlation. Finally, we present tests of our water-optimized functional, that we call vdW-DF-w, showing that it performs very well for a variety of condensed water systems.
Density functional for ternary non-additive hard sphere mixtures.
Schmidt, Matthias
2011-10-19
Based on fundamental measure theory, a Helmholtz free energy density functional for three-component mixtures of hard spheres with general, non-additive interaction distances is constructed. The functional constitutes a generalization of the previously given theory for binary non-additive mixtures. The diagrammatic structure of the spatial integrals in both functionals is of star-like (or tree-like) topology. The ternary diagrams possess a higher degree of complexity than the binary diagrams. Results for partial pair correlation functions, obtained via the Ornstein-Zernike route from the second functional derivatives of the excess free energy functional, agree well with Monte Carlo simulation data. PMID:21946780
Modal density function and number of propagating modes in ducts
NASA Technical Reports Server (NTRS)
Rice, E. J.
1976-01-01
Often raised questions in duct sound propagation studies involve the total number of propagating modes, the number of propagating radial modes for a particular spinning lobe number, and the number of modes possible between two given values of cutoff ratio or eigenvalue. These questions can be answered approximately by using the modal distribution function which is the integral of the modal density function for ducts in a manner similar to that previously published for architectural acoustics. The modal density functions are derived for rectangular and circular ducts with a uniform steady flow. Results from this continuous theory are compared to the actual (discrete) modal distributions.
Van der Waals density functional applied to adsorption systems
NASA Astrophysics Data System (ADS)
Hamada, Ikutaro
2013-03-01
The van der Waals density functional (vdW-DF) is a promising density functional to describe the van der Waals forces within density functional theory. However, despite the recent efforts, there is still room for further improvement, especially for describing molecular adsorption on metal surfaces. I will show that by choosing appropriate exchange and nonlocal correlation functionals, it is possible to calculate geometries and electronic structures for adsorption systems accurately within the framework of vdW-DF. Applicability of the present approach will be illustrated with its applications to graphene/metal, fullerene/metal, and water/graphene interfaces. This work is partly supported by a Grant-in-Aid for Scientific Research on Innovative Area (No. 23104501). AIMR was established by the World Premier International Research Center Initiative (WPI), MEXT, Japan.
A relativistic time-dependent density functional study of the excited states of the mercury dimer.
Kullie, Ossama
2014-01-14
In previous works on Zn2 and Cd2 dimers we found that the long-range corrected CAMB3LYP gives better results than other density functional approximations for the excited states, especially in the asymptotic region. In this paper, we use it to present a time-dependent density functional (TDDFT) study for the ground-state as well as the excited states corresponding to the (6s(2) + 6s6p), (6s(2) + 6s7s), and (6s(2) + 6s7p) atomic asymptotes for the mercury dimer Hg2. We analyze its spectrum obtained from all-electron calculations performed with the relativistic Dirac-Coulomb and relativistic spinfree Hamiltonian as implemented in DIRAC-PACKAGE. A comparison with the literature is given as far as available. Our result is excellent for the most of the lower excited states and very encouraging for the higher excited states, it shows generally good agreements with experimental results and outperforms other theoretical results. This enables us to give a detailed analysis of the spectrum of the Hg2 including a comparative analysis with the lighter dimers of the group 12, Cd2, and Zn2, especially for the relativistic effects, the spin-orbit interaction, and the performance of CAMB3LYP and is enlightened for similar systems. The result shows, as expected, that spinfree Hamiltonian is less efficient than Dirac-Coulomb Hamiltonian for systems containing heavy elements such as Hg2. PMID:24437874
A relativistic time-dependent density functional study of the excited states of the mercury dimer
NASA Astrophysics Data System (ADS)
Kullie, Ossama
2014-01-01
In previous works on Zn2 and Cd2 dimers we found that the long-range corrected CAMB3LYP gives better results than other density functional approximations for the excited states, especially in the asymptotic region. In this paper, we use it to present a time-dependent density functional (TDDFT) study for the ground-state as well as the excited states corresponding to the (6s2 + 6s6p), (6s2 + 6s7s), and (6s2 + 6s7p) atomic asymptotes for the mercury dimer Hg2. We analyze its spectrum obtained from all-electron calculations performed with the relativistic Dirac-Coulomb and relativistic spinfree Hamiltonian as implemented in DIRAC-PACKAGE. A comparison with the literature is given as far as available. Our result is excellent for the most of the lower excited states and very encouraging for the higher excited states, it shows generally good agreements with experimental results and outperforms other theoretical results. This enables us to give a detailed analysis of the spectrum of the Hg2 including a comparative analysis with the lighter dimers of the group 12, Cd2, and Zn2, especially for the relativistic effects, the spin-orbit interaction, and the performance of CAMB3LYP and is enlightened for similar systems. The result shows, as expected, that spinfree Hamiltonian is less efficient than Dirac-Coulomb Hamiltonian for systems containing heavy elements such as Hg2.
Dal Corso, A.; Pasquarello, A.; Baldereschi, A.; Car, R.
1996-01-01
Pseudopotential calculations within density-functional theory for a few selected solids (Si, GaAs, and Al) are used to assess the validity of two generalized-gradient approximations (GGA{close_quote}s), the one proposed by Becke and Perdew (BP) and the more recent one proposed by Perdew and Wang (PW) in comparison with the currently used local-density approximation (LDA). The GGA{close_quote}s give total energies of atoms and cohesive energies of solids that are closer to experiment than the LDA results. Lattice constants are reproduced with the same accuracy as in LDA, while bulk moduli and zone-center phonon frequencies are underestimated with respect to both the LDA and the experimental values. Comparison to all-electron results shows that in both GGA schemes the validity of the pseudopotential approach is as good as in LDA. The predictions of the two GGA{close_quote}s are similar, the PW functional yielding results marginally, but systematically, closer to experiment. The calculated values of the transition pressure in Si between the diamond and the {beta}-tin structure are 72 kbar (LDA), 164 kbar (BP), and 135 kbar (PW), to be compared with the two available experimental values of 103 and 125 kbar. {copyright} {ital 1996 The American Physical Society.}
Force Density Function Relationships in 2-D Granular Media
NASA Technical Reports Server (NTRS)
Youngquist, Robert C.; Metzger, Philip T.; Kilts, Kelly N.
2004-01-01
An integral transform relationship is developed to convert between two important probability density functions (distributions) used in the study of contact forces in granular physics. Developing this transform has now made it possible to compare and relate various theoretical approaches with one another and with the experimental data despite the fact that one may predict the Cartesian probability density and another the force magnitude probability density. Also, the transforms identify which functional forms are relevant to describe the probability density observed in nature, and so the modified Bessel function of the second kind has been identified as the relevant form for the Cartesian probability density corresponding to exponential forms in the force magnitude distribution. Furthermore, it is shown that this transform pair supplies a sufficient mathematical framework to describe the evolution of the force magnitude distribution under shearing. Apart from the choice of several coefficients, whose evolution of values must be explained in the physics, this framework successfully reproduces the features of the distribution that are taken to be an indicator of jamming and unjamming in a granular packing. Key words. Granular Physics, Probability Density Functions, Fourier Transforms
Improved association in a classical density functional theory for water.
Krebs, Eric J; Schulte, Jeff B; Roundy, David
2014-03-28
We present a modification to our recently published statistical associating fluid theory-based classical density functional theory for water. We have recently developed and tested a functional for the averaged radial distribution function at contact of the hard-sphere fluid that is dramatically more accurate at interfaces than earlier approximations. We now incorporate this improved functional into the association term of our free energy functional for water, improving its description of hydrogen bonding. We examine the effect of this improvement by studying two hard solutes (a hard hydrophobic rod and a hard sphere) and a Lennard-Jones approximation of a krypton atom solute. The improved functional leads to a moderate change in the density profile and a large decrease in the number of hydrogen bonds broken in the vicinity of the hard solutes. We find an improvement of the partial radial distribution for a krypton atom in water when compared with experiment. PMID:24697459
Improved association in a classical density functional theory for water
Krebs, Eric J.; Schulte, Jeff B.; Roundy, David
2014-03-28
We present a modification to our recently published statistical associating fluid theory-based classical density functional theory for water. We have recently developed and tested a functional for the averaged radial distribution function at contact of the hard-sphere fluid that is dramatically more accurate at interfaces than earlier approximations. We now incorporate this improved functional into the association term of our free energy functional for water, improving its description of hydrogen bonding. We examine the effect of this improvement by studying two hard solutes (a hard hydrophobic rod and a hard sphere) and a Lennard-Jones approximation of a krypton atom solute. The improved functional leads to a moderate change in the density profile and a large decrease in the number of hydrogen bonds broken in the vicinity of the hard solutes. We find an improvement of the partial radial distribution for a krypton atom in water when compared with experiment.
Rapid Bacterial Detection via an All-Electronic CMOS Biosensor.
Nikkhoo, Nasim; Cumby, Nichole; Gulak, P Glenn; Maxwell, Karen L
2016-01-01
The timely and accurate diagnosis of infectious diseases is one of the greatest challenges currently facing modern medicine. The development of innovative techniques for the rapid and accurate identification of bacterial pathogens in point-of-care facilities using low-cost, portable instruments is essential. We have developed a novel all-electronic biosensor that is able to identify bacteria in less than ten minutes. This technology exploits bacteriocins, protein toxins naturally produced by bacteria, as the selective biological detection element. The bacteriocins are integrated with an array of potassium-selective sensors in Complementary Metal Oxide Semiconductor technology to provide an inexpensive bacterial biosensor. An electronic platform connects the CMOS sensor to a computer for processing and real-time visualization. We have used this technology to successfully identify both Gram-positive and Gram-negative bacteria commonly found in human infections. PMID:27618185
Addressing spectroscopic quality of covariant density functional theory
NASA Astrophysics Data System (ADS)
Afanasjev, A. V.
2015-03-01
The spectroscopic quality of covariant density functional theory has been accessed by analyzing the accuracy and theoretical uncertainties in the description of spectroscopic observables. Such analysis is first presented for the energies of the single-particle states in spherical and deformed nuclei. It is also shown that the inclusion of particle-vibration coupling improves the description of the energies of predominantly single-particle states in medium and heavy-mass spherical nuclei. However, the remaining differences between theory and experiment clearly indicate missing physics and missing terms in covariant energy density functionals. The uncertainties in the predictions of the position of two-neutron drip line sensitively depend on the uncertainties in the prediction of the energies of the single-particle states. On the other hand, many spectroscopic observables in well deformed nuclei at ground state and finite spin only weakly depend on the choice of covariant energy density functional.
Kinetic-energy density functional: Atoms and shell structure
Garcia-Gonzalez, P.; Alvarellos, J.E.; Chacon, E. |
1996-09-01
We present a nonlocal kinetic-energy functional which includes an anisotropic average of the density through a symmetrization procedure. This functional allows a better description of the nonlocal effects of the electron system. The main consequence of the symmetrization is the appearance of a clear shell structure in the atomic density profiles, obtained after the minimization of the total energy. Although previous results with some of the nonlocal kinetic functionals have given incipient structures for heavy atoms, only our functional shows a clear shell structure for most of the atoms. The atomic total energies have a good agreement with the exact calculations. Discussion of the chemical potential and the first ionization potential in atoms is included. The functional is also extended to spin-polarized systems. {copyright} {ital 1996 The American Physical Society.}
Exploration of a modified density dependence in the Skyrme functional
Erler, J.; Reinhard, P.-G.; Kluepfel, P.
2010-10-15
A variant of the basic Skyrme-Hartree-Fock functional is considered dealing with a new form of density dependence. It employs only integer powers and thus will allow a more sound basis for projection schemes (particle number, angular momentum). We optimize the new functional with exactly the same adjustment strategy as used in an earlier study with a standard Skyrme functional. This allows direct comparisons of the performance of the new functional relative to the standard one. We discuss various observables: bulk properties of finite nuclei, nuclear matter, giant resonances, superheavy elements, and energy systematics. The new functional performs at least as well as the standard one, but offers a wider range of applicability (e.g., for projection) and more flexibility in the regime of high densities.
An Accurate Density Functional from Exchange-Correlation Hole
NASA Astrophysics Data System (ADS)
Tao, Jianmin; Mo, Yuxiang
The exchange-correlation hole is most fundamentally important in the development and understanding of density functional theory (DFT). However, due to the nonlocal nature of the exchange-correlation hole, development of DFT from the underlying hole presents a great challenge, and the works along this direction are limited. Here I will discuss a novel nonempirical DFT based on a semilocal hole, which is obtained from the density matrix expansion. Extensive tests on molecules and solids show that this functional can achieve remarkable accuracy for wide-ranging properties in condensed matter physics and quantum chemistry. This work was supported by NSF under Grant No. CHE-1261918.
Nonlinear eigenvalue problems in Density Functional Theory calculations
Fattebert, J
2009-08-28
Developed in the 1960's by W. Kohn and coauthors, Density Functional Theory (DFT) is a very popular quantum model for First-Principles simulations in chemistry and material sciences. It allows calculations of systems made of hundreds of atoms. Indeed DFT reduces the 3N-dimensional Schroedinger electronic structure problem to the search for a ground state electronic density in 3D. In practice it leads to the search for N electronic wave functions solutions of an energy minimization problem in 3D, or equivalently the solution of an eigenvalue problem with a non-linear operator.
Constrained Density Functional Calculations of alpha and delta Pu
NASA Astrophysics Data System (ADS)
Eriksson, Olle
2002-03-01
The electronic structure of α and δ Pu are described using a modified density functional theory that incorporates localization effects of the 5f shell. It is argued that a Russel-Saunders coupled state involving a 5f^4 multiplet, together with one itinerant 5f electron explains most of the observed ground state properties of δ Pu (equilibrium volume, elastic constants, near degeneracy with the alpha phase). This 5f electrons in the α phase are argued to form itinerant states, that are well described in density functional theory. The two distinctly different electronic ground states give rise to different excitation spectra and a comparison with experimental data is made.
Direct propagation of probability density functions in hydrological equations
NASA Astrophysics Data System (ADS)
Kunstmann, Harald; Kastens, Marko
2006-06-01
Sustainable decisions in hydrological risk management require detailed information on the probability density function ( pdf) of the model output. Only then probabilities for the failure of a specific management option or the exceedance of critical thresholds (e.g. of pollutants) can be derived. A new approach of uncertainty propagation in hydrological equations is developed that directly propagates the probability density functions of uncertain model input parameters into the corresponding probability density functions of model output. The basics of the methodology are presented and central applications to different disciplines in hydrology are shown. This work focuses on the following basic hydrological equations: (1) pumping test analysis (Theis-equation, propagation of uncertainties in recharge and transmissivity), (2) 1-dim groundwater contaminant transport equation (Gauss-equation, propagation of uncertainties in decay constant and dispersivity), (3) evapotranspiration estimation (Penman-Monteith-equation, propagation of uncertainty in roughness length). The direct propagation of probability densities is restricted to functions that are monotonically increasing or decreasing or that can be separated in corresponding monotonic branches so that inverse functions can be derived. In case no analytic solutions for inverse functions could be derived, semi-analytical approximations were used. It is shown that the results of direct probability density function propagation are in perfect agreement with results obtained from corresponding Monte Carlo derived frequency distributions. Direct pdf propagation, however, has the advantage that is yields exact solutions for the resulting hydrological pdfs rather than approximating discontinuous frequency distributions. It is additionally shown that the type of the resulting pdf depends on the specific values (order of magnitude, respectively) of the standard deviation of the input pdf. The dependency of skewness and kurtosis
Higher-order adaptive finite-element methods for Kohn–Sham density functional theory
Motamarri, P.; Nowak, M.R.; Leiter, K.; Knap, J.; Gavini, V.
2013-11-15
We present an efficient computational approach to perform real-space electronic structure calculations using an adaptive higher-order finite-element discretization of Kohn–Sham density-functional theory (DFT). To this end, we develop an a priori mesh-adaption technique to construct a close to optimal finite-element discretization of the problem. We further propose an efficient solution strategy for solving the discrete eigenvalue problem by using spectral finite-elements in conjunction with Gauss–Lobatto quadrature, and a Chebyshev acceleration technique for computing the occupied eigenspace. The proposed approach has been observed to provide a staggering 100–200-fold computational advantage over the solution of a generalized eigenvalue problem. Using the proposed solution procedure, we investigate the computational efficiency afforded by higher-order finite-element discretizations of the Kohn–Sham DFT problem. Our studies suggest that staggering computational savings—of the order of 1000-fold—relative to linear finite-elements can be realized, for both all-electron and local pseudopotential calculations, by using higher-order finite-element discretizations. On all the benchmark systems studied, we observe diminishing returns in computational savings beyond the sixth-order for accuracies commensurate with chemical accuracy, suggesting that the hexic spectral-element may be an optimal choice for the finite-element discretization of the Kohn–Sham DFT problem. A comparative study of the computational efficiency of the proposed higher-order finite-element discretizations suggests that the performance of finite-element basis is competing with the plane-wave discretization for non-periodic local pseudopotential calculations, and compares to the Gaussian basis for all-electron calculations to within an order of magnitude. Further, we demonstrate the capability of the proposed approach to compute the electronic structure of a metallic system containing 1688
Higher-order adaptive finite-element methods for Kohn-Sham density functional theory
NASA Astrophysics Data System (ADS)
Motamarri, P.; Nowak, M. R.; Leiter, K.; Knap, J.; Gavini, V.
2013-11-01
We present an efficient computational approach to perform real-space electronic structure calculations using an adaptive higher-order finite-element discretization of Kohn-Sham density-functional theory (DFT). To this end, we develop an a priori mesh-adaption technique to construct a close to optimal finite-element discretization of the problem. We further propose an efficient solution strategy for solving the discrete eigenvalue problem by using spectral finite-elements in conjunction with Gauss-Lobatto quadrature, and a Chebyshev acceleration technique for computing the occupied eigenspace. The proposed approach has been observed to provide a staggering 100-200-fold computational advantage over the solution of a generalized eigenvalue problem. Using the proposed solution procedure, we investigate the computational efficiency afforded by higher-order finite-element discretizations of the Kohn-Sham DFT problem. Our studies suggest that staggering computational savings-of the order of 1000-fold-relative to linear finite-elements can be realized, for both all-electron and local pseudopotential calculations, by using higher-order finite-element discretizations. On all the benchmark systems studied, we observe diminishing returns in computational savings beyond the sixth-order for accuracies commensurate with chemical accuracy, suggesting that the hexic spectral-element may be an optimal choice for the finite-element discretization of the Kohn-Sham DFT problem. A comparative study of the computational efficiency of the proposed higher-order finite-element discretizations suggests that the performance of finite-element basis is competing with the plane-wave discretization for non-periodic local pseudopotential calculations, and compares to the Gaussian basis for all-electron calculations to within an order of magnitude. Further, we demonstrate the capability of the proposed approach to compute the electronic structure of a metallic system containing 1688 atoms using
The exact density functional for two electrons in one dimension
NASA Astrophysics Data System (ADS)
Cohen, Aron; Mori-Sanchez, Paula
The exact universal density functional F [ ρ ] is calculated for real space two-electron densities in one dimension ρ (x) with a soft-Coulomb interaction. It is calculated by the Levy constrained search F [ ρ ] =minΨ-->ρ < Ψ | \\Tcirc +\\Vcircee | Ψ > over wavefunctions of a two-dimensional Hilbert space Ψ (x1 ,x2) --> ρ (x1) and can be directly visualized. We do an approximate constrained search via density matrices and a direct approximation to natural orbitals. This allows us to make an accurate approximation to the exact functional that is calculated using a search over potentials. We investigate the exact functional and the performance of many approximations on some of the most challenging electronic structure in two-electron systems, from strongly-correlated electron transfer to the description of a localized-delocalized transition. The exact Kohn-Sham potential, vs (x) , and exact Kohn-Sham eigenvalues, ɛi, are calculated and this allows us to discuss the band-gap problem versus the perspective of the exact density functional F [ ρ ] for all numbers of electrons. We calculate the derivative discontinuity of the exact functional in an example of a Mott-Insulator, one-dimensional stretched H2.
Bakosi, Jozsef; Ristorcelli, Raymond J
2010-01-01
Probability density function (PDF) methods are extended to variable-density pressure-gradient-driven turbulence. We apply the new method to compute the joint PDF of density and velocity in a non-premixed binary mixture of different-density molecularly mixing fluids under gravity. The full time-evolution of the joint PDF is captured in the highly non-equilibrium flow: starting from a quiescent state, transitioning to fully developed turbulence and finally dissipated by molecular diffusion. High-Atwood-number effects (as distinguished from the Boussinesq case) are accounted for: both hydrodynamic turbulence and material mixing are treated at arbitrary density ratios, with the specific volume, mass flux and all their correlations in closed form. An extension of the generalized Langevin model, originally developed for the Lagrangian fluid particle velocity in constant-density shear-driven turbulence, is constructed for variable-density pressure-gradient-driven flows. The persistent small-scale anisotropy, a fundamentally 'non-Kolmogorovian' feature of flows under external acceleration forces, is captured by a tensorial diffusion term based on the external body force. The material mixing model for the fluid density, an active scalar, is developed based on the beta distribution. The beta-PDF is shown to be capable of capturing the mixing asymmetry and that it can accurately represent the density through transition, in fully developed turbulence and in the decay process. The joint model for hydrodynamics and active material mixing yields a time-accurate evolution of the turbulent kinetic energy and Reynolds stress anisotropy without resorting to gradient diffusion hypotheses, and represents the mixing state by the density PDF itself, eliminating the need for dubious mixing measures. Direct numerical simulations of the homogeneous Rayleigh-Taylor instability are used for model validation.
On the Evolution of the Density Probability Density Function in Strongly Self-gravitating Systems
NASA Astrophysics Data System (ADS)
Girichidis, Philipp; Konstandin, Lukas; Whitworth, Anthony P.; Klessen, Ralf S.
2014-02-01
The time evolution of the probability density function (PDF) of the mass density is formulated and solved for systems in free-fall using a simple approximate function for the collapse of a sphere. We demonstrate that a pressure-free collapse results in a power-law tail on the high-density side of the PDF. The slope quickly asymptotes to the functional form PV (ρ)vpropρ-1.54 for the (volume-weighted) PDF and PM (ρ)vpropρ-0.54 for the corresponding mass-weighted distribution. From the simple approximation of the PDF we derive analytic descriptions for mass accretion, finding that dynamically quiet systems with narrow density PDFs lead to retarded star formation and low star formation rates (SFRs). Conversely, strong turbulent motions that broaden the PDF accelerate the collapse causing a bursting mode of star formation. Finally, we compare our theoretical work with observations. The measured SFRs are consistent with our model during the early phases of the collapse. Comparison of observed column density PDFs with those derived from our model suggests that observed star-forming cores are roughly in free-fall.
On the evolution of the density probability density function in strongly self-gravitating systems
Girichidis, Philipp; Konstandin, Lukas; Klessen, Ralf S.; Whitworth, Anthony P.
2014-02-01
The time evolution of the probability density function (PDF) of the mass density is formulated and solved for systems in free-fall using a simple approximate function for the collapse of a sphere. We demonstrate that a pressure-free collapse results in a power-law tail on the high-density side of the PDF. The slope quickly asymptotes to the functional form P{sub V} (ρ)∝ρ{sup –1.54} for the (volume-weighted) PDF and P{sub M} (ρ)∝ρ{sup –0.54} for the corresponding mass-weighted distribution. From the simple approximation of the PDF we derive analytic descriptions for mass accretion, finding that dynamically quiet systems with narrow density PDFs lead to retarded star formation and low star formation rates (SFRs). Conversely, strong turbulent motions that broaden the PDF accelerate the collapse causing a bursting mode of star formation. Finally, we compare our theoretical work with observations. The measured SFRs are consistent with our model during the early phases of the collapse. Comparison of observed column density PDFs with those derived from our model suggests that observed star-forming cores are roughly in free-fall.
All-electron scalar relativistic calculation of water molecule adsorption onto small gold clusters.
Kuang, Xiang-Jun; Wang, Xin-Qiang; Liu, Gao-Bin
2011-08-01
An all-electron scalar relativistic calculation was performed on Au( n )H(2)O (n = 1-13) clusters using density functional theory (DFT) with the generalized gradient approximation at PW91 level. The calculation results reveal that, after adsorption, the small gold cluster would like to bond with oxygen and the H(2)O molecule prefers to occupy the single fold coordination site. Reflecting the strong scalar relativistic effect, Au( n ) geometries are distorted slightly but still maintain a planar structure. The Au-Au bond is strengthened and the H-O bond is weakened, as manifested by the shortening of the Au-Au bond-length and the lengthening of the H-O bond-length. The H-O-H bond angle becomes slightly larger. The enhancement of reactivity of the H(2)O molecule is obvious. The Au-O bond-lengths, adsorption energies, VIPs, HLGs, HOMO (LUMO) energy levels, charge transfers and the highest vibrational frequencies of the Au-O mode for Au( n )H(2)O clusters exhibit an obvious odd-even oscillation. The most favorable adsorption between small gold clusters and the H(2)O molecule takes place when the H(2)O molecule is adsorbed onto an even-numbered Au( n ) cluster and becomes an Au( n )H(2)O cluster with an even number of valence electrons. The odd-even alteration of magnetic moments is observed in Au( n )H(2)O clusters and may serve as material with a tunable code capacity of "0" and "1" by adsorbing a H(2)O molecule onto an odd or even-numbered small gold cluster. PMID:21140279
Subsystem real-time time dependent density functional theory
NASA Astrophysics Data System (ADS)
Krishtal, Alisa; Ceresoli, Davide; Pavanello, Michele
2015-04-01
We present the extension of Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) to real-time Time Dependent Density Functional Theory (rt-TDDFT). FDE is a DFT-in-DFT embedding method that allows to partition a larger Kohn-Sham system into a set of smaller, coupled Kohn-Sham systems. Additional to the computational advantage, FDE provides physical insight into the properties of embedded systems and the coupling interactions between them. The extension to rt-TDDFT is done straightforwardly by evolving the Kohn-Sham subsystems in time simultaneously, while updating the embedding potential between the systems at every time step. Two main applications are presented: the explicit excitation energy transfer in real time between subsystems is demonstrated for the case of the Na4 cluster and the effect of the embedding on optical spectra of coupled chromophores. In particular, the importance of including the full dynamic response in the embedding potential is demonstrated.
External orthogonality in subsystem time-dependent density functional theory.
Chulhai, Dhabih V; Jensen, Lasse
2016-08-01
Subsystem density functional theory (subsystem DFT) is a DFT partitioning method that is exact in principle, but depends on approximations to the kinetic energy density functional (KEDF). One may avoid the use of approximate KEDFs by ensuring that the inter-subsystem molecular orbitals are orthogonal, termed external orthogonality (EO). We present a method that extends a subsystem DFT method, that includes EO, into the time-dependent DFT (TDDFT) regime. This method therefore removes the need for approximations to the kinetic energy potential and kernel, and we show that it can accurately reproduce the supermolecular TDDFT results for weakly and strongly coupled subsystems, and for systems with strongly overlapping densities (where KEDF approximations traditionally fail). PMID:26932176
Applying Density Functional Theory for Atomic Vacancies in Solids
NASA Astrophysics Data System (ADS)
Zhou, Xiaolan; Perdew, John P.
2008-03-01
We use a new generalized gradient approximation of density functional theory -- PBEsol, a revised Perdew-Burke-Ernzerhof GGA, to calculate the vacancy formation energies and other properties of metals and semiconductors: Al, Pt, Pd, GaN [1], etc. By restoring the gradient expansion over a wide range of density gradients, PBEsol [2] yields excellent jellium exchange and correlation surface energies. We expect that this new functional will improve the description of vacancies in real materials, since the vacancy formation energy is essentially the work needed to create an interior surface. [1] Thomas R.Mattsson and Ann E. Mattson. Phys. Rev. B 66, 214410 (2002). [2] John P. Perdew, Adrienn Ruzsinszky, Gabor I. Csonka, Oleg A. Vydrov, Gustavo E. Scuseria, Lucian A. Constantin, Xiaolan Zhou, and Kieron Burke, Restoring the density-gradient expansion for exchange in solids and surfaces, http://arxiv.org/abs/0711.0156
Catalytic activities of platinum nanotubes: a density functional study
NASA Astrophysics Data System (ADS)
Mukherjee, Prajna; Gupta, Bikash C.; Jena, Puru
2015-10-01
In this work we investigate the catalytic properties of platinum nanotubes using density functional theory based calculations. In particular, we study the dissociation of hydrogen and oxygen molecules as well as oxidation of CO molecules. The results indicate that platinum nanotubes have good catalytic properties and can be effectively used in converting CO molecule to CO2.
NASA Astrophysics Data System (ADS)
Manzhos, Sergei
2016-01-01
A comparative DFTB (density functional tight binding)-DFT (density functional theory) study of several adsorption modes of 2-anthroic acid on titania is presented. Two parameterizations of DFTB previously used for dye-TiO2 interfaces are tested. DFTB predicts adsorption energies which differ from those computed by DFT not only in magnitude (by up to 0.5 eV) but also in the order among different configurations. The band alignment computed with DFTB is not consistent with DFT results and with experimental data. The strategy of geometry optimization with DFTB followed by single-point DFT calculations also does not necessarily result in plausible adsorption energies.
NASA Astrophysics Data System (ADS)
Vidya, R.; Ravindran, P.; Fjellvåg, H.; Svensson, B. G.; Monakhov, E.; Ganchenkova, M.; Nieminen, R. M.
2011-01-01
Formation energies of various intrinsic defects and defect complexes in ZnO have been calculated using a density-functional-theory-based pseudopotential all-electron method. The various defects considered are oxygen vacancy (VO), zinc vacancy (VZn), oxygen at an interstitial site (Oi), Zn at an interstitial site (Zni), Zn at VO (ZnO), O at VZn(OZn), and an antisite pair (combination of the preceding two defects). In addition, defect complexes like (VO+Zni) and Zn-vacancy clusters are studied. The Schokkty pair (VO+VZn) and Frenkel pairs [(VO+Oi) and (VZn+Zni)] are considered theoretically for the first time. Upon comparing the formation energies of these defects, we find that VO would be the dominant intrinsic defect under both Zn-rich and O-rich conditions and it is a deep double donor. Both ZnO and Zni are found to be shallow donors. The low formation energy of donor-type intrinsic defects could lead to difficulty in achieving p-type conductivity in ZnO. Defect complexes have charge transitions deep inside the band gap. The red, yellow, and green photoluminescence peaks of undoped samples can be assigned to some of the defect complexes considered. It is believed that the red luminescence originates from an electronic transition in VO, but we find that it can originate from the antisite ZnO defect. Charge density and electron-localization function analyses have been used to understand the effect of these defects on the ZnO lattice. The electronic structure of ZnO with intrinsic defects has been studied using density-of-states and electronic band structure plots. The acceptor levels introduced by VZn are relatively localized, making it difficult to achieve p-type conductivity with sufficient hole mobility.
Reduced density-matrix functionals applied to the Hubbard dimer
NASA Astrophysics Data System (ADS)
Kamil, Ebad; Schade, Robert; Pruschke, Thomas; Blöchl, Peter E.
2016-02-01
Common density-matrix functionals, the Müller and the power functional, have been benchmarked for the half-filled Hubbard dimer, which allows us to model the bond dissociation problem and the transition from the weakly to the strongly correlated limit. Unbiased numerical calculations are combined with analytical results. Despite the well known successes of the Müller functional, the ground state is degenerate with a one-dimensional manifold of ferromagnetic solutions. The resulting infinite magnetic susceptibility indicates another qualitative flaw of the Müller functional. The derivative discontinuity with respect to particle number is not present indicating an incorrect metal-like behavior. The power functional actually favors the ferromagnetic state for weak interaction. Analogous to the Hartree-Fock approximation, the power functional undergoes a transition beyond a critical interaction strength, in this case, however, to a noncollinear antiferromagnetic state.
Density Functional Study of Perovskite Superconductor MgCNi3
NASA Astrophysics Data System (ADS)
Kumar, Jagdish; Sharma, Devina; Kumar, Ranjan; Awana, V. P. S.; Ahluwalia, P. K.
2011-12-01
We here report the first principle density functional study of MgCNi3 which crystallize in cubic perovskite structure having critical transition temperature of 8 K. The interesting aspect of this compound is that in normal state it is non magnetic in nature despite conduction electrons in it are derived from partially filled Ni d states, which typically lead to ferromagnetism in metallic Ni and many Ni-based binary alloys. To investigate the detailed microscopic origin of the non magnetic nature we have done density functional based calculations on this compound. The lattice constant is calculated using minimum energy criteria from total energy versus lattice constant plot. By taking the calculated values of lattice constant we have done the precise calculations on the compound using Full Potential Linear Augmented Plane Wave (FP-LAPW) method implemented in ELK code. The electronic density of states is found spin degenerate that corresponds to a non-magnetic ground state. The density of states (DOS) at Fermi level, N(EF) is dominated by Ni-d states. The sharp peak observed just below Fermi level corresponds to van Hove singularity (vHs). The projected density of states (PDOS) suggests a strong hybridization of Ni-3d and C-2p states which is responsible for the observed non magnetic nature of MgCNi3.
Density functional calculations of point defects in InAs
NASA Astrophysics Data System (ADS)
Moussa, Jonathan; Schultz, Peter
2013-03-01
Standard semilocal density functionals do not generate a gap in the Kohn-Sham eigenvalues for InAs, a semiconductor with an experimental gap of 0.4 eV. Without a theoretical band gap, it becomes difficult to identify, specify, and characterize pure localized states of point defects with energy levels within the experimental band gap. The bulk band gap problem can be alleviated with screened hybrid density functionals, such as the Heyd-Scuseria-Ernzerhof (HSE) functional, that open the generalized Kohn-Sham eigenvalue gap of InAs to near the experimental value. However, even without a Kohn-Sham gap, the local moment countercharge (LMCC) method [Phys. Rev. Lett. 96, 246401 (2006)] is able to predict charge transition energy levels of localized defect states, using standard semi-local functionals. We present an LMCC-based study of standard point defects in InAs using semilocal density functionals and compare the results to HSE-based calculations to assess the validity of LMCC calculations in this situation. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DOE's National Nuclear Security Administration under contract DE-AC04-94AL85000.
Density Functional Theory of Biologically Relevant Metal Centers
NASA Astrophysics Data System (ADS)
Siegbahn, Per E. M.; Blomberg, Margareta R. A.
1999-10-01
Recent applications of density functional theory to biologically relevant metal centers are reviewed. The emphasis is on reaction mechanisms, structures, and modeling. The accuracy of different functionals is discussed for standard benchmark tests of first- and second-row molecules and for transition metal systems. Modeling aspects of the protein metal complexes are discussed regarding both the size of the model being treated quantum mechanically and the treatment of the protein surrounding it. To illustrate the effects, structures computed without the effects of the protein are compared with experimental structures from enzymes, and results from simple dielectric models of the protein for electron transfer processes are described. The choice of spin state is discussed for multimetal complexes. Examples of mechanisms studied recently by density functional theory are described, such as O2 and methane activation in methane monooxygenase and O2 formation in photosystem II.
Ab initio derivation of model energy density functionals
NASA Astrophysics Data System (ADS)
Dobaczewski, Jacek
2016-08-01
I propose a simple and manageable method that allows for deriving coupling constants of model energy density functionals (EDFs) directly from ab initio calculations performed for finite fermion systems. A proof-of-principle application allows for linking properties of finite nuclei, determined by using the nuclear nonlocal Gogny functional, to the coupling constants of the quasilocal Skyrme functional. The method does not rely on properties of infinite fermion systems but on the ab initio calculations in finite systems. It also allows for quantifying merits of different model EDFs in describing the ab initio results.
Perspective: Fundamental aspects of time-dependent density functional theory
NASA Astrophysics Data System (ADS)
Maitra, Neepa T.
2016-06-01
In the thirty-two years since the birth of the foundational theorems, time-dependent density functional theory has had a tremendous impact on calculations of electronic spectra and dynamics in chemistry, biology, solid-state physics, and materials science. Alongside the wide-ranging applications, there has been much progress in understanding fundamental aspects of the functionals and the theory itself. This Perspective looks back to some of these developments, reports on some recent progress and current challenges for functionals, and speculates on future directions to improve the accuracy of approximations used in this relatively young theory.
Partial ionization in dense plasmas: comparisons among average-atom density functional models.
Murillo, Michael S; Weisheit, Jon; Hansen, Stephanie B; Dharma-wardana, M W C
2013-06-01
Nuclei interacting with electrons in dense plasmas acquire electronic bound states, modify continuum states, generate resonances and hopping electron states, and generate short-range ionic order. The mean ionization state (MIS), i.e, the mean charge Z of an average ion in such plasmas, is a valuable concept: Pseudopotentials, pair-distribution functions, equations of state, transport properties, energy-relaxation rates, opacity, radiative processes, etc., can all be formulated using the MIS of the plasma more concisely than with an all-electron description. However, the MIS does not have a unique definition and is used and defined differently in different statistical models of plasmas. Here, using the MIS formulations of several average-atom models based on density functional theory, we compare numerical results for Be, Al, and Cu plasmas for conditions inclusive of incomplete atomic ionization and partial electron degeneracy. By contrasting modern orbital-based models with orbital-free Thomas-Fermi models, we quantify the effects of shell structure, continuum resonances, the role of exchange and correlation, and the effects of different choices of the fundamental cell and boundary conditions. Finally, the role of the MIS in plasma applications is illustrated in the context of x-ray Thomson scattering in warm dense matter. PMID:23848795
Gonis, A.; Zhang, X. G.; Stocks, G. M.; Nicholson, D. M.
2015-10-23
Density functional theory for the case of general, N-representable densities is reformulated in terms of density functional derivatives of expectation values of operators evaluated with wave functions leading to a density, making no reference to the concept of potential. The developments provide a complete solution of the v-representability problem by establishing a mathematical procedure that determines whether a density is v-representable and in the case of an affirmative answer determines the potential (within an additive constant) as a derivative with respect to the density of a constrained search functional. It also establishes the existence of an energy functional of the density that, for v-representable densities, assumes its minimum value at the density describing the ground state of an interacting many-particle system. The theorems of Hohenberg and Kohn emerge as special cases of the formalism.
Gonis, A.; Zhang, X. G.; Stocks, G. M.; Nicholson, D. M.
2015-10-23
Density functional theory for the case of general, N-representable densities is reformulated in terms of density functional derivatives of expectation values of operators evaluated with wave functions leading to a density, making no reference to the concept of potential. The developments provide a complete solution of the v-representability problem by establishing a mathematical procedure that determines whether a density is v-representable and in the case of an affirmative answer determines the potential (within an additive constant) as a derivative with respect to the density of a constrained search functional. It also establishes the existence of an energy functional of themore » density that, for v-representable densities, assumes its minimum value at the density describing the ground state of an interacting many-particle system. The theorems of Hohenberg and Kohn emerge as special cases of the formalism.« less
Modal density function and number of propagating modes in ducts
NASA Technical Reports Server (NTRS)
Rice, E. J.
1976-01-01
The question of the number of propagating modes within a small range of mode cut off ratio was raised. The population density of modes were shown to be greatest near cut off and least for the well propagating modes. It was shown that modes of nearly the same cut off ratio behave nearly the same in a sound absorbing duct as well as in the way they propagate to the far. Handling all of the propagating modes individually, they can be grouped into several cut off ratio ranges. It is important to know the modal density function to estimate acoustic power distribution.
Numerical density-to-potential inversions in time-dependent density functional theory.
Jensen, Daniel S; Wasserman, Adam
2016-08-01
We treat the density-to-potential inverse problem of time-dependent density functional theory as an optimization problem with a partial differential equation constraint. The unknown potential is recovered from a target density by applying a multilevel optimization method controlled by error estimates. We employ a classical optimization routine using gradients efficiently computed by the discrete adjoint method. The inverted potential has both a real and imaginary part to reduce reflections at the boundaries and other numerical artifacts. We demonstrate this method on model one-dimensional systems. The method can be straightforwardly extended to a variety of numerical solvers of the time-dependent Kohn-Sham equations and to systems in higher dimensions. PMID:26984427
SURFACE SYMMETRY ENERGY OF NUCLEAR ENERGY DENSITY FUNCTIONALS
Nikolov, N; Schunck, N; Nazarewicz, W; Bender, M; Pei, J
2010-12-20
We study the bulk deformation properties of the Skyrme nuclear energy density functionals. Following simple arguments based on the leptodermous expansion and liquid drop model, we apply the nuclear density functional theory to assess the role of the surface symmetry energy in nuclei. To this end, we validate the commonly used functional parametrizations against the data on excitation energies of superdeformed band-heads in Hg and Pb isotopes, and fission isomers in actinide nuclei. After subtracting shell effects, the results of our self-consistent calculations are consistent with macroscopic arguments and indicate that experimental data on strongly deformed configurations in neutron-rich nuclei are essential for optimizing future nuclear energy density functionals. The resulting survey provides a useful benchmark for further theoretical improvements. Unlike in nuclei close to the stability valley, whose macroscopic deformability hangs on the balance of surface and Coulomb terms, the deformability of neutron-rich nuclei strongly depends on the surface-symmetry energy; hence, its proper determination is crucial for the stability of deformed phases of the neutron-rich matter and description of fission rates for r-process nucleosynthesis.
Steady-State Density Functional Theory for Finite Bias Conductances.
Stefanucci, G; Kurth, S
2015-12-01
In the framework of density functional theory, a formalism to describe electronic transport in the steady state is proposed which uses the density on the junction and the steady current as basic variables. We prove that, in a finite window around zero bias, there is a one-to-one map between the basic variables and both local potential on as well as bias across the junction. The resulting Kohn-Sham system features two exchange-correlation (xc) potentials, a local xc potential, and an xc contribution to the bias. For weakly coupled junctions the xc potentials exhibit steps in the density-current plane which are shown to be crucial to describe the Coulomb blockade diamonds. At small currents these steps emerge as the equilibrium xc discontinuity bifurcates. The formalism is applied to a model benzene junction, finding perfect agreement with the orthodox theory of Coulomb blockade. PMID:26571349
Computational complexity of time-dependent density functional theory
NASA Astrophysics Data System (ADS)
Whitfield, J. D.; Yung, M.-H.; Tempel, D. G.; Boixo, S.; Aspuru-Guzik, A.
2014-08-01
Time-dependent density functional theory (TDDFT) is rapidly emerging as a premier method for solving dynamical many-body problems in physics and chemistry. The mathematical foundations of TDDFT are established through the formal existence of a fictitious non-interacting system (known as the Kohn-Sham system), which can reproduce the one-electron reduced probability density of the actual system. We build upon these works and show that on the interior of the domain of existence, the Kohn-Sham system can be efficiently obtained given the time-dependent density. We introduce a V-representability parameter which diverges at the boundary of the existence domain and serves to quantify the numerical difficulty of constructing the Kohn-Sham potential. For bounded values of V-representability, we present a polynomial time quantum algorithm to generate the time-dependent Kohn-Sham potential with controllable error bounds.
Scrutinizing "Invisible" astatine: A challenge for modern density functionals.
Sergentu, Dumitru-Claudiu; David, Grégoire; Montavon, Gilles; Maurice, Rémi; Galland, Nicolas
2016-06-01
The main-group 6p elements did not receive much attention in the development of recent density functionals. In many cases it is still difficult to choose among the modern ones a relevant functional for various applications. Here, we illustrate the case of astatine species (At, Z = 85) and we report the first, and quite complete, benchmark study on several properties concerning such species. Insights on geometries, transition energies and thermodynamic properties of a set of 19 astatine species, for which reference experimental or theoretical data has been reported, are obtained with relativistic (two-component) density functional theory calculations. An extensive set of widely used functionals is employed. The hybrid meta-generalized gradient approximation (meta-GGA) PW6B95 functional is overall the best choice. It is worth noting that the range-separated HSE06 functional as well as the old and very popular B3LYP and PBE0 hybrid-GGAs appear to perform quite well too. Moreover, we found that astatine chemistry in solution can accurately be predicted using implicit solvent models, provided that specific parameters are used to build At cavities. © 2016 Wiley Periodicals, Inc. PMID:27059181
What Density Functional Theory could do for Quantum Information
NASA Astrophysics Data System (ADS)
Mattsson, Ann
2015-03-01
The Hohenberg-Kohn theorem of Density Functional Theory (DFT), and extensions thereof, tells us that all properties of a system of electrons can be determined through their density, which uniquely determines the many-body wave-function. Given access to the appropriate, universal, functionals of the density we would, in theory, be able to determine all observables of any electronic system, without explicit reference to the wave-function. On the other hand, the wave-function is at the core of Quantum Information (QI), with the wave-function of a set of qubits being the central computational resource in a quantum computer. While there is seemingly little overlap between DFT and QI, reliance upon observables form a key connection. Though the time-evolution of the wave-function and associated phase information is fundamental to quantum computation, the initial and final states of a quantum computer are characterized by observables of the system. While observables can be extracted directly from a system's wave-function, DFT tells us that we may be able to intuit a method for extracting them from its density. In this talk, I will review the fundamentals of DFT and how these principles connect to the world of QI. This will range from DFT's utility in the engineering of physical qubits, to the possibility of using it to efficiently (but approximately) simulate Hamiltonians at the logical level. The apparent paradox of describing algorithms based on the quantum mechanical many-body wave-function with a DFT-like theory based on observables will remain a focus throughout. The ultimate goal of this talk is to initiate a dialog about what DFT could do for QI, in theory and in practice. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
Dynamical density functional theory for colloidal dispersions including hydrodynamic interactions
NASA Astrophysics Data System (ADS)
Rex, M.; Löwen, H.
2009-02-01
A dynamical density functional theory (DDFT) for translational Brownian dynamics is derived which includes hydrodynamic interactions. The theory reduces to the simple Brownian DDFT proposed by Marconi and Tarazona (U. Marini Bettolo Marconi and P. Tarazona, J. Chem. Phys. 110, 8032 (1999); J. Phys.: Condens. Matter 12, A413 (2000)) when hydrodynamic interactions are neglected. The derivation is based on Smoluchowski’s equation for the time evolution of the probability density with pairwise hydrodynamic interactions. The theory is applied to hard-sphere colloids in an oscillating spherical optical trap which switches periodically in time from a stable confining to an unstable potential. Rosenfeld’s fundamental measure theory for the equilibrium density functional is used and hydrodynamics are incorporated on the Rotne-Prager level. The results for the time-dependent density profiles are compared to extensive Brownian dynamics simulations which are performed on the same Rotne-Prager level and excellent agreement is obtained. It is further found that hydrodynamic interactions damp and slow the dynamics of the confined colloid cluster in comparison to the same situation with neglected hydrodynamic interactions.
Precise effective masses from density functional perturbation theory
NASA Astrophysics Data System (ADS)
Laflamme Janssen, J.; Gillet, Y.; Poncé, S.; Martin, A.; Torrent, M.; Gonze, X.
2016-05-01
The knowledge of effective masses is a key ingredient to analyze numerous properties of semiconductors, like carrier mobilities, (magneto)transport properties, or band extrema characteristics yielding carrier densities and density of states. Currently, these masses are usually calculated using finite-difference estimation of density functional theory (DFT) electronic band curvatures. However, finite differences require an additional convergence study and are prone to numerical noise. Moreover, the concept of effective mass breaks down at degenerate band extrema. We assess the former limitation by developing a method that allows to obtain the Hessian of DFT bands directly, using density functional perturbation theory. Then, we solve the latter issue by adapting the concept of "transport equivalent effective mass" to the k .p ̂ framework. The numerical noise inherent to finite-difference methods is thus eliminated, along with the associated convergence study. The resulting method is therefore more general, more robust, and simpler to use, which makes it especially appropriate for high-throughput computing. After validating the developed techniques, we apply them to the study of silicon, graphane, and arsenic. The formalism is implemented into the abinit software and supports the norm-conserving pseudopotential approach, the projector augmented-wave method, and the inclusion of spin-orbit coupling. The derived expressions also apply to the ultrasoft pseudopotential method.
Density Functional Theory for Steady-State Nonequilibrium Molecular Junctions
NASA Astrophysics Data System (ADS)
Liu, Shuanglong; Nurbawono, Argo; Zhang, Chun
2015-10-01
We present a density functional theory (DFT) for steady-state nonequilibrium quantum systems such as molecular junctions under a finite bias. Based on the steady-state nonequilibrium statistics that maps nonequilibrium to an effective equilibrium, we show that ground-state DFT (GS-DFT) is not applicable in this case and two densities, the total electron density and the density of current-carrying electrons, are needed to uniquely determine the properties of the corresponding nonequilibrium system. A self-consistent mean-field approach based on two densities is then derived. The theory is implemented into SIESTA computational package and applied to study nonequilibrium electronic/transport properties of a realistic carbon-nanotube (CNT)/Benzene junction. Results obtained from our steady-state DFT (SS-DFT) are compared with those of conventional GS-DFT based transport calculations. We show that SS-DFT yields energetically more stable nonequilibrium steady state, predicts significantly lower electric current, and is able to produce correct electronic structures in local equilibrium under a limiting case.
Semilocal density functional theory with correct surface asymptotics
NASA Astrophysics Data System (ADS)
Constantin, Lucian A.; Fabiano, Eduardo; Pitarke, J. M.; Della Sala, Fabio
2016-03-01
Semilocal density functional theory is the most used computational method for electronic structure calculations in theoretical solid-state physics and quantum chemistry of large systems, providing good accuracy with a very attractive computational cost. Nevertheless, because of the nonlocality of the exchange-correlation hole outside a metal surface, it was always considered inappropriate to describe the correct surface asymptotics. Here, we derive, within the semilocal density functional theory formalism, an exact condition for the imagelike surface asymptotics of both the exchange-correlation energy per particle and potential. We show that this condition can be easily incorporated into a practical computational tool, at the simple meta-generalized-gradient approximation level of theory. Using this tool, we also show that the Airy-gas model exhibits asymptotic properties that are closely related to those at metal surfaces. This result highlights the relevance of the linear effective potential model to the metal surface asymptotics.
Excitations and benchmark ensemble density functional theory for two electrons
Pribram-Jones, Aurora; Burke, Kieron; Yang, Zeng-hui; Ullrich, Carsten A.; Trail, John R.; Needs, Richard J.
2014-05-14
A new method for extracting ensemble Kohn-Sham potentials from accurate excited state densities is applied to a variety of two-electron systems, exploring the behavior of exact ensemble density functional theory. The issue of separating the Hartree energy and the choice of degenerate eigenstates is explored. A new approximation, spin eigenstate Hartree-exchange, is derived. Exact conditions that are proven include the signs of the correlation energy components and the asymptotic behavior of the potential for small weights of the excited states. Many energy components are given as a function of the weights for two electrons in a one-dimensional flat box, in a box with a large barrier to create charge transfer excitations, in a three-dimensional harmonic well (Hooke's atom), and for the He atom singlet-triplet ensemble, singlet-triplet-singlet ensemble, and triplet bi-ensemble.
Analyzing the financial crisis using the entropy density function
NASA Astrophysics Data System (ADS)
Oh, Gabjin; Kim, Ho-yong; Ahn, Seok-Won; Kwak, Wooseop
2015-02-01
The risk that is created by nonlinear interactions among subjects in economic systems is assumed to increase during an abnormal state of a financial market. Nevertheless, investigating the systemic risk in financial markets following the global financial crisis is not sufficient. In this paper, we analyze the entropy density function in the return time series for several financial markets, such as the S&P500, KOSPI, and DAX indices, from October 2002 to December 2011 and analyze the variability in the entropy value over time. We find that the entropy density function of the S&P500 index during the subprime crisis exhibits a significant decrease compared to that in other periods, whereas the other markets, such as those in Germany and Korea, exhibit no significant decrease during the market crisis. These findings demonstrate that the S&P500 index generated a regular pattern in the return time series during the financial crisis.
Covariant density functional theory: The role of the pion
Lalazissis, G. A.; Karatzikos, S.; Serra, M.; Otsuka, T.; Ring, P.
2009-10-15
We investigate the role of the pion in covariant density functional theory. Starting from conventional relativistic mean field (RMF) theory with a nonlinear coupling of the {sigma} meson and without exchange terms we add pions with a pseudovector coupling to the nucleons in relativistic Hartree-Fock approximation. In order to take into account the change of the pion field in the nuclear medium the effective coupling constant of the pion is treated as a free parameter. It is found that the inclusion of the pion to this sort of density functionals does not destroy the overall description of the bulk properties by RMF. On the other hand, the noncentral contribution of the pion (tensor coupling) does have effects on single particle energies and on binding energies of certain nuclei.
Neutrinoless double-beta decay in covariant density functional theory
Ring, P.; Yao, J. M.; Song, L. S.; Hagino, K.; Meng, J.
2015-10-15
We use covariant density functional theory beyond mean field in order to describe neutrinoless double-beta decay in a fully relativistic way. The dynamic effects of particle-number and angular-momentum conservations as well as shape fluctuations of quadrupole character are taken into account within the generator coordinate method for both initial and final nuclei. The calculations are based on the full relativistic transition operator. The nuclear matrix elements (NME’s) for a large number of possible transitions are investigated. The results are compared with various non-relativistic calculations, in particular also with the density functional theory based on the Gogny force. We find that the non-relativistic approximation is justified and that the total NME’s can be well approximated by the pure axial-vector coupling term. This corresponds to a considerable reduction of the computational effort.
Density-functional theory of inhomogeneous systems of hard spherocylinders
Velasco; Mederos; Sullivan
2000-09-01
The smectic-A phase boundaries of a hard-spherocylinder fluid are calculated using a density-functional theory based on one proposed earlier by Somoza and Tarazona [Phys. Rev. A 41, 965 (1990)]. Our calculations do not employ the translation-rotation decoupling approximation used in previous density-functional theories. The calculated phase boundaries agree well with computer simulation results up to aspect ratios L/D approximately 5 and are in better agreement with the simulations than are previous theories. We generalize the model fluid by including long-range interactions with quadrupolar orientational symmetry, which are taken into account by mean-field approximation. For sufficiently large strength, these interactions produce a smectic-C phase, which undergoes either a continuous or weakly first-order transition to the smectic-A phase. The theory and numerical methods discussed here can be applied to the analysis of interfacial phenomena. PMID:11088887
Neutrinoless double-beta decay in covariant density functional theory
NASA Astrophysics Data System (ADS)
Ring, P.; Yao, J. M.; Song, L. S.; Hagino, K.; Meng, J.
2015-10-01
We use covariant density functional theory beyond mean field in order to describe neutrinoless double-beta decay in a fully relativistic way. The dynamic effects of particle-number and angular-momentum conservations as well as shape fluctuations of quadrupole character are taken into account within the generator coordinate method for both initial and final nuclei. The calculations are based on the full relativistic transition operator. The nuclear matrix elements (NME's) for a large number of possible transitions are investigated. The results are compared with various non-relativistic calculations, in particular also with the density functional theory based on the Gogny force. We find that the non-relativistic approximation is justified and that the total NME's can be well approximated by the pure axial-vector coupling term. This corresponds to a considerable reduction of the computational effort.
Density versus spin-density functional in DFT+U and DFT+DMFT
NASA Astrophysics Data System (ADS)
Park, Hyowon; Millis, Andrew; Marianetti, Chris
2015-03-01
The construction of multi-variable effective action theories such as DFT+U and DFT+DMFT requires the choice of a local subspace of correlated orbitals and an additional variable being either the charge density or spin density. This talk examines the differences between using charge-only and spin-dependent exchange-correlation functionals with the aim of providing guidance for constructing more sophisticated beyond-density functional theories. The widely used spin-dependent approximations to the exchange-correlation functional are found to lead to a large and in some cases unphysical effective exchange coupling within the correlated subspace. Additionally, the differences between Wannier and Projector based definitions of the correlated orbitals are examined, and only small differences are found provided that the orbitals are orthonormal and strongly localized. These results are documented in the context of the rare earth nickelates. This work is supported under the Grant DOE-ER-046169 and under the FAME grant, one of six centers of STARnet, a Semiconductor Research Corporation program sponsored by MARCO and DARPA.
Śmiga, Szymon; Fabiano, Eduardo; Laricchia, Savio; Constantin, Lucian A; Della Sala, Fabio
2015-04-21
We analyze the methodology and the performance of subsystem density functional theory (DFT) with meta-generalized gradient approximation (meta-GGA) exchange-correlation functionals for non-bonded molecular systems. Meta-GGA functionals depend on the Kohn-Sham kinetic energy density (KED), which is not known as an explicit functional of the density. Therefore, they cannot be directly applied in subsystem DFT calculations. We propose a Laplacian-level approximation to the KED which overcomes this limitation and provides a simple and accurate way to apply meta-GGA exchange-correlation functionals in subsystem DFT calculations. The so obtained density and energy errors, with respect to the corresponding supermolecular calculations, are comparable with conventional approaches, depending almost exclusively on the approximations in the non-additive kinetic embedding term. An embedding energy error decomposition explains the accuracy of our method. PMID:25903880
Autoionization in time-dependent density-functional theory
NASA Astrophysics Data System (ADS)
Kapoor, V.
2016-06-01
We compute the exact exchange-correlation potential of the time-dependent density-functional theory (TDDFT) for the correlated process of autoionization. The potential develops barriers which regulate the autoionization rate. TDDFT employing known and practicable exchange-correlation potentials does not capture any autoionization dynamics. Approximate exchange-correlation potentials capturing such dynamics would necessarily require memory effects and are unlikely to be developed, as will be illustrated.
Density functional theory across chemistry, physics and biology
van Mourik, Tanja; Bühl, Michael; Gaigeot, Marie-Pierre
2014-01-01
The past decades have seen density functional theory (DFT) evolve from a rising star in computational quantum chemistry to one of its major players. This Theme Issue, which comes half a century after the publication of the Hohenberg–Kohn theorems that laid the foundations of modern DFT, reviews progress and challenges in present-day DFT research. Rather than trying to be comprehensive, this Theme Issue attempts to give a flavour of selected aspects of DFT. PMID:24516181
Association between lung function and airway wall density
NASA Astrophysics Data System (ADS)
Leader, J. Ken; Zheng, Bin; Fuhrman, Carl R.; Tedrow, John; Park, Sang C.; Tan, Jun; Pu, Jiantao; Drescher, John M.; Gur, David; Sciurba, Frank C.
2009-02-01
Computed tomography (CT) examination is often used to quantify the relation between lung function and airway remodeling in chronic obstructive pulmonary disease (COPD). In this preliminary study, we examined the association between lung function and airway wall computed attenuation ("density") in 200 COPD screening subjects. Percent predicted FVC (FVC%), percent predicted FEV1 (FEV1%), and the ratio of FEV1 to FVC as a percentage (FEV1/FVC%) were measured post-bronchodilator. The apical bronchus of the right upper lobe was manually selected from CT examinations for evaluation. Total airway area, lumen area, wall area, lumen perimeter and wall area as fraction of the total airway area were computed. Mean HU (meanHU) and maximum HU (maxHU) values were computed across pixels assigned membership in the wall and with a HU value greater than -550. The Pearson correlation coefficients (PCC) between FVC%, FEV1%, and FEV1/FVC% and meanHU were -0.221 (p = 0.002), -0.175 (p = 0.014), and -0.110 (p = 0.123), respectively. The PCCs for maxHU were only significant for FVC%. The correlations between lung function and the airway morphometry parameters were slightly stronger compared to airway wall density. MeanHU was significantly correlated with wall area (PCC = 0.720), airway area (0.498) and wall area percent (0.611). This preliminary work demonstrates that airway wall density is associated with lung function. Although the correlations in our study were weaker than a recent study, airway wall density initially appears to be an important parameter in quantitative CT analysis of COPD.
Probability Density Function Method for Langevin Equations with Colored Noise
Wang, Peng; Tartakovsky, Alexandre M.; Tartakovsky, Daniel M.
2013-04-05
We present a novel method to derive closed-form, computable PDF equations for Langevin systems with colored noise. The derived equations govern the dynamics of joint or marginal probability density functions (PDFs) of state variables, and rely on a so-called Large-Eddy-Diffusivity (LED) closure. We demonstrate the accuracy of the proposed PDF method for linear and nonlinear Langevin equations, describing the classical Brownian displacement and dispersion in porous media.
Density functional theory across chemistry, physics and biology.
van Mourik, Tanja; Bühl, Michael; Gaigeot, Marie-Pierre
2014-03-13
The past decades have seen density functional theory (DFT) evolve from a rising star in computational quantum chemistry to one of its major players. This Theme Issue, which comes half a century after the publication of the Hohenberg-Kohn theorems that laid the foundations of modern DFT, reviews progress and challenges in present-day DFT research. Rather than trying to be comprehensive, this Theme Issue attempts to give a flavour of selected aspects of DFT. PMID:24516181
Probability density function modeling for sub-powered interconnects
NASA Astrophysics Data System (ADS)
Pater, Flavius; Amaricǎi, Alexandru
2016-06-01
This paper proposes three mathematical models for reliability probability density function modeling the interconnect supplied at sub-threshold voltages: spline curve approximations, Gaussian models,and sine interpolation. The proposed analysis aims at determining the most appropriate fitting for the switching delay - probability of correct switching for sub-powered interconnects. We compare the three mathematical models with the Monte-Carlo simulations of interconnects for 45 nm CMOS technology supplied at 0.25V.
Next generation high density self assembling functional protein arrays
Ramachandran, Niroshan; Raphael, Jacob V.; Hainsworth, Eugenie; Demirkan, Gokhan; Fuentes, Manuel G.; Rolfs, Andreas; Hu, Yanhui; LaBaer, Joshua
2009-01-01
We report a high-density self assembling protein microarray that displays thousands of proteins, produced and captured in situ from immobilized cDNA templates. Over 1500 unique cDNAs were tested with > 90% success with nearly all proteins displaying yields within 2 fold of the mean, minimal sample variation and good day to day reproducibility. The displayed proteins revealed selective protein interactions. This method will enable various experimental approaches to study protein function in high throughput. PMID:18469824
Plato: A localised orbital based density functional theory code
NASA Astrophysics Data System (ADS)
Kenny, S. D.; Horsfield, A. P.
2009-12-01
The Plato package allows both orthogonal and non-orthogonal tight-binding as well as density functional theory (DFT) calculations to be performed within a single framework. The package also provides extensive tools for analysing the results of simulations as well as a number of tools for creating input files. The code is based upon the ideas first discussed in Sankey and Niklewski (1989) [1] with extensions to allow high-quality DFT calculations to be performed. DFT calculations can utilise either the local density approximation or the generalised gradient approximation. Basis sets from minimal basis through to ones containing multiple radial functions per angular momenta and polarisation functions can be used. Illustrations of how the package has been employed are given along with instructions for its utilisation. Program summaryProgram title: Plato Catalogue identifier: AEFC_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEFC_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 219 974 No. of bytes in distributed program, including test data, etc.: 1 821 493 Distribution format: tar.gz Programming language: C/MPI and PERL Computer: Apple Macintosh, PC, Unix machines Operating system: Unix, Linux and Mac OS X Has the code been vectorised or parallelised?: Yes, up to 256 processors tested RAM: Up to 2 Gbytes per processor Classification: 7.3 External routines: LAPACK, BLAS and optionally ScaLAPACK, BLACS, PBLAS, FFTW Nature of problem: Density functional theory study of electronic structure and total energies of molecules, crystals and surfaces. Solution method: Localised orbital based density functional theory. Restrictions: Tight-binding and density functional theory only, no exact exchange. Unusual features: Both atom centred and uniform meshes available
Advances in time-dependent current-density functional theory
NASA Astrophysics Data System (ADS)
Berger, Arjan
In this work we solve the problem of the gauge dependence of molecular magnetic properties (magnetizabilities, circular dichroism) using time-dependent current-density functional theory [1]. We also present a new functional that accurately describes the optical absorption spectra of insulators, semiconductors and metals [2] N. Raimbault, P.L. de Boeij, P. Romaniello, and J.A. Berger Phys. Rev. Lett. 114, 066404 (2015) J.A. Berger, Phys. Rev. Lett. 115, 137402 (2015) This study has been partially supported through the Grant NEXT No. ANR-10-LABX-0037 in the framework of the Programme des Investissements d'Avenir.
Thermal Corrections to Density Functional Simulations of Warm Dense Matter
NASA Astrophysics Data System (ADS)
Smith, Justin; Pribram-Jones, Aurora; Burke, Kieron
Present density functional calculations of warm dense matter often use the Mermin-Kohn-Sham (MKS) scheme at finite temperature, but employ ground-state approximations to the exchange-correlation (XC) free energy. In the simplest solvable non-trivial model, an asymmetric Hubbard dimer, we calculate the exact many-body energies, the exact Mermin-Kohn-Sham functionals for this system, and extract the exact XC free energy. For moderate temperatures and weak correlation, we show this approximation is excellent, but fails for stronger correlations. Additionally, we use this system to test various conditions that must be satisfied.
Linear Scaling Density Functional Calculations with Gaussian Orbitals
NASA Technical Reports Server (NTRS)
Scuseria, Gustavo E.
1999-01-01
Recent advances in linear scaling algorithms that circumvent the computational bottlenecks of large-scale electronic structure simulations make it possible to carry out density functional calculations with Gaussian orbitals on molecules containing more than 1000 atoms and 15000 basis functions using current workstations and personal computers. This paper discusses the recent theoretical developments that have led to these advances and demonstrates in a series of benchmark calculations the present capabilities of state-of-the-art computational quantum chemistry programs for the prediction of molecular structure and properties.
Conformational Analysis of Thioether Musks Using Density Functional Theory
Setzer, William N.
2009-01-01
A conformational analysis of nine macrocyclic thioether musks has been carried out using molecular mechanics (MMFF), density functional theory (DFT) using both B3LYP and M06 functionals, as well as Hartree-Fock and post-Hartree-Fock (MP2) ab initio methods. 6-Thia-, 10-thia- and 4-methyl-5-thia-14-tetradecananolide, 4-thia-, 7-thia-, 11-thia- and 12-thia-15-pentadecanolide and 6-thia- and 12-thia-16-hexadecanolide were modeled. Unfortunately, there was little agreement between the computational methods at the levels of theory used in this study. PMID:20111690
Atomistic force field for alumina fit to density functional theory
Sarsam, Joanne; Finnis, Michael W.; Tangney, Paul
2013-11-28
We present a force field for bulk alumina (Al{sub 2}O{sub 3}), which has been parametrized by fitting the energies, forces, and stresses of a large database of reference configurations to those calculated with density functional theory (DFT). We use a functional form that is simpler and computationally more efficient than some existing models of alumina parametrized by a similar technique. Nevertheless, we demonstrate an accuracy of our potential that is comparable to those existing models and to DFT. We present calculations of crystal structures and energies, elastic constants, phonon spectra, thermal expansion, and point defect formation energies.
Franco-Pérez, Marco; Ayers, Paul W; Gázquez, José L; Vela, Alberto
2015-12-28
We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model. PMID:26723661
Franco-Pérez, Marco E-mail: ayers@mcmaster.ca E-mail: avela@cinvestav.mx; Ayers, Paul W. E-mail: ayers@mcmaster.ca E-mail: avela@cinvestav.mx; Gázquez, José L. E-mail: ayers@mcmaster.ca E-mail: avela@cinvestav.mx; Vela, Alberto E-mail: ayers@mcmaster.ca E-mail: avela@cinvestav.mx
2015-12-28
We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model.
A Wigner Monte Carlo approach to density functional theory
NASA Astrophysics Data System (ADS)
Sellier, J. M.; Dimov, I.
2014-08-01
In order to simulate quantum N-body systems, stationary and time-dependent density functional theories rely on the capacity of calculating the single-electron wave-functions of a system from which one obtains the total electron density (Kohn-Sham systems). In this paper, we introduce the use of the Wigner Monte Carlo method in ab-initio calculations. This approach allows time-dependent simulations of chemical systems in the presence of reflective and absorbing boundary conditions. It also enables an intuitive comprehension of chemical systems in terms of the Wigner formalism based on the concept of phase-space. Finally, being based on a Monte Carlo method, it scales very well on parallel machines paving the way towards the time-dependent simulation of very complex molecules. A validation is performed by studying the electron distribution of three different systems, a Lithium atom, a Boron atom and a hydrogenic molecule. For the sake of simplicity, we start from initial conditions not too far from equilibrium and show that the systems reach a stationary regime, as expected (despite no restriction is imposed in the choice of the initial conditions). We also show a good agreement with the standard density functional theory for the hydrogenic molecule. These results demonstrate that the combination of the Wigner Monte Carlo method and Kohn-Sham systems provides a reliable computational tool which could, eventually, be applied to more sophisticated problems.
Density functional theory and chromium: Insights from the dimers
Würdemann, Rolf; Kristoffersen, Henrik H.; Moseler, Michael; Walter, Michael
2015-03-28
The binding in small Cr clusters is re-investigated, where the correct description of the dimer in three charge states is used as criterion to assign the most suitable density functional theory approximation. The difficulty in chromium arises from the subtle interplay between energy gain from hybridization and energetic cost due to exchange between s and d based molecular orbitals. Variations in published bond lengths and binding energies are shown to arise from insufficient numerical representation of electron density and Kohn-Sham wave-functions. The best functional performance is found for gradient corrected (GGA) functionals and meta-GGAs, where we find severe differences between functionals from the same family due to the importance of exchange. Only the “best fit” from Bayesian error estimation is able to predict the correct energetics for all three charge states unambiguously. With this knowledge, we predict small bond-lengths to be exclusively present in Cr{sub 2} and Cr{sub 2}{sup −}. Already for the dimer cation, solely long bond-lengths appear, similar to what is found in the trimer and in chromium bulk.
Curvature and Frontier Orbital Energies in Density Functional Theory
Stein, Tamar; Autschbach, Jochen; Govind, Niranjan; Kronik, Leeor; Baer, Roi
2012-12-20
Perdew et al. [Phys. Rev. Lett 49, 1691 (1982)] discovered and proved two different properties that exact Kohn-Sham density functional theory (DFT) must obey: (i) The exact total energy versus particle number must be a series of linear segments between integer electron points; (ii) Across an integer number of electrons, the exchange-correlation potential may ``jump’’ by a constant, known as the derivative discontinuity (DD). Here, we show analytically that in both the original and the generalized Kohn-Sham formulation of DFT, the two are in fact two sides of the same coin. Absence of a derivative discontinuity necessitates deviation from piecewise linearity, and the latter can be used to correct for the former, thereby restoring the physical meaning of the orbital energies. Using selected small molecules, we show that this results in a simple correction scheme for any underlying functional, including semi-local and hybrid functionals as well as Hartree-Fock theory, suggesting a practical correction for the infamous gap problem of density functional theory. Moreover, we show that optimally-tuned range-separated hybrid functionals can inherently minimize both DD and curvature, thus requiring no correction, and show that this can be used as a sound theoretical basis for novel tuning strategies.
Van der Waals Density Functional Theory with Applications
NASA Astrophysics Data System (ADS)
Langreth, David C.
2004-03-01
We discuss the development of electronic density functionals that are applicable for weakly bound systems where the van der Waals interaction and its ramifications become important. Our current functionals approach the correct asymptotic dependence at large distances and are seamless at small distances. The first form of the functional, appropriate for layered systems, has been recently applied to graphite, boron nitride, and molybdenum sulfide [H. Rydberg et al., Phys. Rev. Lett. 91, 126402 (2003) and D. C. Langreth, Int. J. Quant. Chem. (submitted), see http//:www.physics.rutgers.edu/ ˜langreth/preprints/dft2003.pdf]. The second form of the functional [M. Dion it et al. (to be published)] is appropriate for arbitrary geometries. Recent results on rare gas dimers and the benzene dimer suggest promise for this method as well.
A relativistic time-dependent density functional study of the excited states of the mercury dimer
Kullie, Ossama E-mail: ossama.kullie@unistra.fr
2014-01-14
In previous works on Zn{sub 2} and Cd{sub 2} dimers we found that the long-range corrected CAMB3LYP gives better results than other density functional approximations for the excited states, especially in the asymptotic region. In this paper, we use it to present a time-dependent density functional (TDDFT) study for the ground-state as well as the excited states corresponding to the (6s{sup 2} + 6s6p), (6s{sup 2} + 6s7s), and (6s{sup 2} + 6s7p) atomic asymptotes for the mercury dimer Hg{sub 2}. We analyze its spectrum obtained from all-electron calculations performed with the relativistic Dirac-Coulomb and relativistic spinfree Hamiltonian as implemented in DIRAC-PACKAGE. A comparison with the literature is given as far as available. Our result is excellent for the most of the lower excited states and very encouraging for the higher excited states, it shows generally good agreements with experimental results and outperforms other theoretical results. This enables us to give a detailed analysis of the spectrum of the Hg{sub 2} including a comparative analysis with the lighter dimers of the group 12, Cd{sub 2}, and Zn{sub 2}, especially for the relativistic effects, the spin-orbit interaction, and the performance of CAMB3LYP and is enlightened for similar systems. The result shows, as expected, that spinfree Hamiltonian is less efficient than Dirac-Coulomb Hamiltonian for systems containing heavy elements such as Hg{sub 2}.
Generalized Pauli constraints in reduced density matrix functional theory
Theophilou, Iris; Helbig, Nicole; Lathiotakis, Nektarios N.; Marques, Miguel A. L.
2015-04-21
Functionals of the one-body reduced density matrix (1-RDM) are routinely minimized under Coleman’s ensemble N-representability conditions. Recently, the topic of pure-state N-representability conditions, also known as generalized Pauli constraints, received increased attention following the discovery of a systematic way to derive them for any number of electrons and any finite dimensionality of the Hilbert space. The target of this work is to assess the potential impact of the enforcement of the pure-state conditions on the results of reduced density-matrix functional theory calculations. In particular, we examine whether the standard minimization of typical 1-RDM functionals under the ensemble N-representability conditions violates the pure-state conditions for prototype 3-electron systems. We also enforce the pure-state conditions, in addition to the ensemble ones, for the same systems and functionals and compare the correlation energies and optimal occupation numbers with those obtained by the enforcement of the ensemble conditions alone.
Density-dependence of functional spiking networks in vitro
Ham, Michael I; Gintautuas, Vadas; Rodriguez, Marko A; Bettencourt, Luis M A; Bennett, Ryan; Santa Maria, Cara L
2008-01-01
During development, the mammalian brain differentiates into specialized regions with unique functional abilities. While many factors contribute to this functional specialization, we explore the effect neuronal density can have on neuronal interactions. Two types of networks, dense (50,000 neurons and glia support cells) and sparse (12,000 neurons and glia support cells), are studied. A competitive first response model is applied to construct activation graphs that represent pairwise neuronal interactions. By observing the evolution of these graphs during development in vitro we observe that dense networks form activation connections earlier than sparse networks, and that link-!llltropy analysis of the resulting dense activation graphs reveals that balanced directional connections dominate. Information theoretic measures reveal in addition that early functional information interactions (of order 3) are synergetic in both dense and sparse networks. However, during development in vitro, such interactions become redundant in dense, but not sparse networks. Large values of activation graph link-entropy correlate strongly with redundant ensembles observed in the dense networks. Results demonstrate differences between dense and sparse networks in terms of informational groups, pairwise relationships, and activation graphs. These differences suggest that variations in cell density may result in different functional specialization of nervous system tissue also in vivo.
Downlink Probability Density Functions for EOS-McMurdo Sound
NASA Technical Reports Server (NTRS)
Christopher, P.; Jackson, A. H.
1996-01-01
The visibility times and communication link dynamics for the Earth Observations Satellite (EOS)-McMurdo Sound direct downlinks have been studied. The 16 day EOS periodicity may be shown with the Goddard Trajectory Determination System (GTDS) and the entire 16 day period should be simulated for representative link statistics. We desire many attributes of the downlink, however, and a faster orbital determination method is desirable. We use the method of osculating elements for speed and accuracy in simulating the EOS orbit. The accuracy of the method of osculating elements is demonstrated by closely reproducing the observed 16 day Landsat periodicity. An autocorrelation function method is used to show the correlation spike at 16 days. The entire 16 day record of passes over McMurdo Sound is then used to generate statistics for innage time, outage time, elevation angle, antenna angle rates, and propagation loss. The levation angle probability density function is compared with 1967 analytic approximation which has been used for medium to high altitude satellites. One practical result of this comparison is seen to be the rare occurrence of zenith passes. The new result is functionally different than the earlier result, with a heavy emphasis on low elevation angles. EOS is one of a large class of sun synchronous satellites which may be downlinked to McMurdo Sound. We examine delay statistics for an entire group of sun synchronous satellites ranging from 400 km to 1000 km altitude. Outage probability density function results are presented three dimensionally.
Revealing the density of encoded functions in a viral RNA
Patel, Nikesh; Dykeman, Eric C.; Coutts, Robert H. A.; Lomonossoff, George P.; Rowlands, David J.; Phillips, Simon E. V.; Ranson, Neil; Twarock, Reidun; Tuma, Roman; Stockley, Peter G.
2015-01-01
We present direct experimental evidence that assembly of a single-stranded RNA virus occurs via a packaging signal-mediated mechanism. We show that the sequences of coat protein recognition motifs within multiple, dispersed, putative RNA packaging signals, as well as their relative spacing within a genomic fragment, act collectively to influence the fidelity and yield of capsid self-assembly in vitro. These experiments confirm that the selective advantages for viral yield and encapsidation specificity, predicted from previous modeling of packaging signal-mediated assembly, are found in Nature. Regions of the genome that act as packaging signals also function in translational and transcriptional enhancement, as well as directly coding for the coat protein, highlighting the density of encoded functions within the viral RNA. Assembly and gene expression are therefore direct molecular competitors for different functional folds of the same RNA sequence. The strongest packaging signal in the test fragment, encodes a region of the coat protein that undergoes a conformational change upon contact with packaging signals. A similar phenomenon occurs in other RNA viruses for which packaging signals are known. These contacts hint at an even deeper density of encoded functions in viral RNA, which if confirmed, would have profound consequences for the evolution of this class of pathogens. PMID:25646435
Current density partitioning in time-dependent current density functional theory
Mosquera, Martín A.; Wasserman, Adam; Department of Physics, Purdue University, West Lafayette, Indiana 47907
2014-05-14
We adapt time-dependent current density functional theory to allow for a fragment-based solution of the many-electron problem of molecules in the presence of time-dependent electric and magnetic fields. Regarding a molecule as a set of non-interacting subsystems that individually evolve under the influence of an auxiliary external electromagnetic vector-scalar potential pair, the partition 4-potential, we show that there are one-to-one mappings between this auxiliary potential, a sharply-defined set of fragment current densities, and the total current density of the system. The partition electromagnetic (EM) 4-potential is expressed in terms of the real EM 4-potential of the system and a gluing EM 4-potential that accounts for exchange-correlation effects and mutual interaction forces between fragments that are required to yield the correct electron dynamics. We prove the zero-force theorem for the fragmented system, establish a variational formulation in terms of action functionals, and provide a simple illustration for a charged particle in a ring.
Storchi, Loriano; Rampino, Sergio; Belpassi, Leonardo; Tarantelli, Francesco; Quiney, Harry M
2013-12-10
We propose a new complete memory-distributed algorithm, which significantly improves the parallel implementation of the all-electron four-component Dirac-Kohn-Sham (DKS) module of BERTHA (J. Chem. Theory Comput. 2010, 6, 384). We devised an original procedure for mapping the DKS matrix between an efficient integral-driven distribution, guided by the structure of specific G-spinor basis sets and by density fitting algorithms, and the two-dimensional block-cyclic distribution scheme required by the ScaLAPACK library employed for the linear algebra operations. This implementation, because of the efficiency in the memory distribution, represents a leap forward in the applicability of the DKS procedure to arbitrarily large molecular systems and its porting on last-generation massively parallel systems. The performance of the code is illustrated by some test calculations on several gold clusters of increasing size. The DKS self-consistent procedure has been explicitly converged for two representative clusters, namely Au20 and Au34, for which the density of electronic states is reported and discussed. The largest gold cluster uses more than 39k basis functions and DKS matrices of the order of 23 GB. PMID:26592273
Stochastic Optimally Tuned Range-Separated Hybrid Density Functional Theory.
Neuhauser, Daniel; Rabani, Eran; Cytter, Yael; Baer, Roi
2016-05-19
We develop a stochastic formulation of the optimally tuned range-separated hybrid density functional theory that enables significant reduction of the computational effort and scaling of the nonlocal exchange operator at the price of introducing a controllable statistical error. Our method is based on stochastic representations of the Coulomb convolution integral and of the generalized Kohn-Sham density matrix. The computational cost of the approach is similar to that of usual Kohn-Sham density functional theory, yet it provides a much more accurate description of the quasiparticle energies for the frontier orbitals. This is illustrated for a series of silicon nanocrystals up to sizes exceeding 3000 electrons. Comparison with the stochastic GW many-body perturbation technique indicates excellent agreement for the fundamental band gap energies, good agreement for the band edge quasiparticle excitations, and very low statistical errors in the total energy for large systems. The present approach has a major advantage over one-shot GW by providing a self-consistent Hamiltonian that is central for additional postprocessing, for example, in the stochastic Bethe-Salpeter approach. PMID:26651840
Density functional theory: Its origins, rise to prominence, and future
NASA Astrophysics Data System (ADS)
Jones, R. O.
2015-07-01
In little more than 20 years, the number of applications of the density functional (DF) formalism in chemistry and materials science has grown in an astonishing fashion. The number of publications alone shows that DF calculations make up a huge success story, and many younger colleagues are surprised to learn that the widespread application of density functional methods, particularly in chemistry, began only after 1990. This is indeed unexpected, because the origins are usually traced to the papers of Hohenberg, Kohn, and Sham more than a quarter of a century earlier. The DF formalism, its applications, and prospects were reviewed for this journal in 1989. About the same time, the combination of DF calculations with molecular dynamics promised to provide an efficient way to study structures and reactions in molecules and extended systems. This paper reviews the development of density-related methods back to the early years of quantum mechanics and follows the breakthrough in their application after 1990. The two examples from biochemistry and materials science are among the many current applications that were simply far beyond expectations in 1990. The reasons why—50 years after its modern formulation and after two decades of rapid expansion—some of the most cited practitioners in the field are concerned about its future are discussed.
Subsystem real-time time dependent density functional theory.
Krishtal, Alisa; Ceresoli, Davide; Pavanello, Michele
2015-04-21
We present the extension of Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) to real-time Time Dependent Density Functional Theory (rt-TDDFT). FDE is a DFT-in-DFT embedding method that allows to partition a larger Kohn-Sham system into a set of smaller, coupled Kohn-Sham systems. Additional to the computational advantage, FDE provides physical insight into the properties of embedded systems and the coupling interactions between them. The extension to rt-TDDFT is done straightforwardly by evolving the Kohn-Sham subsystems in time simultaneously, while updating the embedding potential between the systems at every time step. Two main applications are presented: the explicit excitation energy transfer in real time between subsystems is demonstrated for the case of the Na4 cluster and the effect of the embedding on optical spectra of coupled chromophores. In particular, the importance of including the full dynamic response in the embedding potential is demonstrated. PMID:25903875
Applications of large-scale density functional theory in biology
NASA Astrophysics Data System (ADS)
Cole, Daniel J.; Hine, Nicholas D. M.
2016-10-01
Density functional theory (DFT) has become a routine tool for the computation of electronic structure in the physics, materials and chemistry fields. Yet the application of traditional DFT to problems in the biological sciences is hindered, to a large extent, by the unfavourable scaling of the computational effort with system size. Here, we review some of the major software and functionality advances that enable insightful electronic structure calculations to be performed on systems comprising many thousands of atoms. We describe some of the early applications of large-scale DFT to the computation of the electronic properties and structure of biomolecules, as well as to paradigmatic problems in enzymology, metalloproteins, photosynthesis and computer-aided drug design. With this review, we hope to demonstrate that first principles modelling of biological structure-function relationships are approaching a reality.
Applications of large-scale density functional theory in biology.
Cole, Daniel J; Hine, Nicholas D M
2016-10-01
Density functional theory (DFT) has become a routine tool for the computation of electronic structure in the physics, materials and chemistry fields. Yet the application of traditional DFT to problems in the biological sciences is hindered, to a large extent, by the unfavourable scaling of the computational effort with system size. Here, we review some of the major software and functionality advances that enable insightful electronic structure calculations to be performed on systems comprising many thousands of atoms. We describe some of the early applications of large-scale DFT to the computation of the electronic properties and structure of biomolecules, as well as to paradigmatic problems in enzymology, metalloproteins, photosynthesis and computer-aided drug design. With this review, we hope to demonstrate that first principles modelling of biological structure-function relationships are approaching a reality. PMID:27494095
Van der Waals Interactions in Density Functional Theory: Intermolecular Complexes
NASA Astrophysics Data System (ADS)
Kannemann, Felix; Becke, Axel
2010-03-01
Conventional density functional theory (GGA and hybrid functionals) fails to account for dispersion interactions and is therefore not applicable to systems where van der Waals interactions play a dominant role, such as intermolecular complexes and biomolecules. The exchange-hole dipole moment (XDM) dispersion model of Becke and Johnson [A. D. Becke and E. R. Johnson, J. Chem. Phys. 127, 154108 (2007)] corrects for this deficiency. We have previously shown that the XDM dispersion model can be combined with standard GGA functionals (PW86 for exchange and PBE for correlation) to give accurate binding energy curves for rare-gas diatomics [F. O. Kannemann and A. D. Becke, J. Chem. Theory Comput. 5, 719 (2009)]. Here we present further tests of the GGA-XDM method using benchmark sets including hydrogen bonding, electrostatic, dispersion and stacking interactions, and systems ranging from rare-gas diatomics to biomolecular complexes.
Dipole polarizability of 120Sn and nuclear energy density functionals
NASA Astrophysics Data System (ADS)
Hashimoto, T.; Krumbholz, A. M.; Reinhard, P.-G.; Tamii, A.; von Neumann-Cosel, P.; Adachi, T.; Aoi, N.; Bertulani, C. A.; Fujita, H.; Fujita, Y.; GanioÇ§lu, E.; Hatanaka, K.; Ideguchi, E.; Iwamoto, C.; Kawabata, T.; Khai, N. T.; Krugmann, A.; Martin, D.; Matsubara, H.; Miki, K.; Neveling, R.; Okamura, H.; Ong, H. J.; Poltoratska, I.; Ponomarev, V. Yu.; Richter, A.; Sakaguchi, H.; Shimbara, Y.; Shimizu, Y.; Simonis, J.; Smit, F. D.; Süsoy, G.; Suzuki, T.; Thies, J. H.; Yosoi, M.; Zenihiro, J.
2015-09-01
The electric dipole strength distribution in 120Sn between 5 and 22 MeV has been determined at the Research Center for Nuclear Physics, Osaka, from polarization transfer observables measured in proton inelastic scattering at E0=295 MeV and forward angles including 0∘. Combined with photoabsorption data, a highly precise electric dipole polarizability αD(120Sn) =8.93 (36 ) fm3 is extracted. The dipole polarizability as isovector observable par excellence carries direct information on nuclear symmetry energy and its density dependence. The correlation of the new value with the well-established αD(208Pb) serves as a test of its prediction by nuclear energy density functionals. Models based on modern Skyrme interactions describe the data fairly well while most calculations based on relativistic Hamiltonians cannot.
Dynamic density functional theory of solid tumor growth: Preliminary models.
Chauviere, Arnaud; Hatzikirou, Haralambos; Kevrekidis, Ioannis G; Lowengrub, John S; Cristini, Vittorio
2012-03-01
Cancer is a disease that can be seen as a complex system whose dynamics and growth result from nonlinear processes coupled across wide ranges of spatio-temporal scales. The current mathematical modeling literature addresses issues at various scales but the development of theoretical methodologies capable of bridging gaps across scales needs further study. We present a new theoretical framework based on Dynamic Density Functional Theory (DDFT) extended, for the first time, to the dynamics of living tissues by accounting for cell density correlations, different cell types, phenotypes and cell birth/death processes, in order to provide a biophysically consistent description of processes across the scales. We present an application of this approach to tumor growth. PMID:22489279
Sublinear scaling for time-dependent stochastic density functional theory
Gao, Yi; Neuhauser, Daniel; Baer, Roi; Rabani, Eran
2015-01-21
A stochastic approach to time-dependent density functional theory is developed for computing the absorption cross section and the random phase approximation (RPA) correlation energy. The core idea of the approach involves time-propagation of a small set of stochastic orbitals which are first projected on the occupied space and then propagated in time according to the time-dependent Kohn-Sham equations. The evolving electron density is exactly represented when the number of random orbitals is infinite, but even a small number (≈16) of such orbitals is enough to obtain meaningful results for absorption spectrum and the RPA correlation energy per electron. We implement the approach for silicon nanocrystals using real-space grids and find that the overall scaling of the algorithm is sublinear with computational time and memory.
Hubbard operator density functional theory for Fermionic lattice models
NASA Astrophysics Data System (ADS)
Cheng, Zhengqian; Marianetti, Chris
We formulate an effective action as a functional of Hubbard operator densities whose stationary point delivers all local static information of the interacting lattice model. Using the variational principle, we get a self-consistent equation for Hubbard operator densities. The computational cost of our approach is set by diagonalizing the local Fock space. We apply our method to the one and two band Hubbard model (including crystal field and on-site exchange) in infinite dimensions where the exact solution is known. Excellent agreement is obtained for the one-band model. In the two-band model, good agreement is obtained in the metallic region of the phase diagram in addition to the metal-insulator transition. While our approach does not address frequency dependent observables, it has a negligible computational cost as compared to dynamical mean field theory and could be highly applicable in the context total energies of strongly correlated materials and molecules.
Density Functional Calculations for Atoms, Molecules and Clusters
NASA Astrophysics Data System (ADS)
Gunnarsson, O.; Jones, R. O.
1980-01-01
The density functional formalism provides a framework for including exchange and correlation effects in the calculation of ground state properties of many-electron systems. The reduction of the problem to the solution of single-particle equations leads to important numerical advantages over other ab initio methods of incorporating correlation effects. The essential features of the scheme are outlined and results obtained for atomic and molecular systems are surveyed. The local spin density (LSD) approximation gives generally good results for systems where the bonding involves s and p electrons, but results are less satisfactory for d-bonded systems. Non-local modifications to the LSD approximation have been tested on atomic systems yielding much improved total energies.
Relativistic density functional theory for finite nuclei and neutron stars
NASA Astrophysics Data System (ADS)
Piekarewicz, Jorge
In 1939 Oppenheimer and Volkoff demonstrated using Einstein's theory of general relativity that a neutron star supported exclusively by neutron degeneracy pressure will collapse into a black hole if its mass exceeds seven tenths of a solar mass. Seventy five years after such a pioneering prediction the existence of neutron stars with masses as large as two solar masses has been firmly established. This fact alone highlights the critical role that nuclear interactions play in explaining the structure of neutron stars. Indeed, a neutron star is a gold mine for the study of nuclear phenomena that span an enormous range of densities and neutron-proton asymmetries. Physical phenomena over such diverse scales are best described by a formalism based on Relativistic Density Functional Theory. In this contribution I focus on the synergy between theory, experiment, and observation that is needed to elucidate the myriad of exotic states of matter that are believed to exist in a neutron star.
Nuclear chiral and magnetic rotation in covariant density functional theory
NASA Astrophysics Data System (ADS)
Meng, Jie; Zhao, Pengwei
2016-05-01
Excitations of chiral rotation observed in triaxial nuclei and magnetic and/or antimagnetic rotations (AMR) seen in near-spherical nuclei have attracted a lot of attention. Unlike conventional rotation in well-deformed or superdeformed nuclei, here the rotational axis is not necessary coinciding with any principal axis of the nuclear density distribution. Thus, tilted axis cranking (TAC) is mandatory to describe these excitations self-consistently in the framework of covariant density functional theory (CDFT). We will briefly introduce the formalism of TAC–CDFT and its application for magnetic and AMR phenomena. Configuration-fixed CDFT and its predictions for nuclear chiral configurations and for favorable triaxial deformation parameters are also presented, and the discoveries of the multiple chiral doublets in 133Ce and 103Rh are discussed.
Sissay, Adonay; Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J; Lopata, Kenneth
2016-09-01
Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals. PMID:27608987
Progress at the interface of wave-function and density-functional theories
Gidopoulos, Nikitas I.
2011-04-15
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 Schroedinger (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.
Characterizing the Spatial Density Functions of Neural Arbors
NASA Astrophysics Data System (ADS)
Teeter, Corinne Michelle
Recently, it has been proposed that a universal function describes the way in which all arbors (axons and dendrites) spread their branches over space. Data from fish retinal ganglion cells as well as cortical and hippocampal arbors from mouse, rat, cat, monkey and human provide evidence that all arbor density functions (adf) can be described by a Gaussian function truncated at approximately two standard deviations. A Gaussian density function implies that there is a minimal set of parameters needed to describe an adf: two or three standard deviations (depending on the dimensionality of the arbor) and an amplitude. However, the parameters needed to completely describe an adf could be further constrained by a scaling law found between the product of the standard deviations and the amplitude of the function. In the following document, I examine the scaling law relationship in order to determine the minimal set of parameters needed to describe an adf. First, I find that the at, two-dimensional arbors of fish retinal ganglion cells require only two out of the three fundamental parameters to completely describe their density functions. Second, the three-dimensional, volume filling, cortical arbors require four fundamental parameters: three standard deviations and the total length of an arbor (which corresponds to the amplitude of the function). Next, I characterize the shape of arbors in the context of the fundamental parameters. I show that the parameter distributions of the fish retinal ganglion cells are largely homogenous. In general, axons are bigger and less dense than dendrites; however, they are similarly shaped. The parameter distributions of these two arbor types overlap and, therefore, can only be differentiated from one another probabilistically based on their adfs. Despite artifacts in the cortical arbor data, different types of arbors (apical dendrites, non-apical dendrites, and axons) can generally be differentiated based on their adfs. In addition, within
SUMO1 Affects Synaptic Function, Spine Density and Memory
Matsuzaki, Shinsuke; Lee, Linda; Knock, Erin; Srikumar, Tharan; Sakurai, Mikako; Hazrati, Lili-Naz; Katayama, Taiichi; Staniszewski, Agnieszka; Raught, Brian; Arancio, Ottavio; Fraser, Paul E.
2015-01-01
Small ubiquitin-like modifier-1 (SUMO1) plays a number of roles in cellular events and recent evidence has given momentum for its contributions to neuronal development and function. Here, we have generated a SUMO1 transgenic mouse model with exclusive overexpression in neurons in an effort to identify in vivo conjugation targets and the functional consequences of their SUMOylation. A high-expressing line was examined which displayed elevated levels of mono-SUMO1 and increased high molecular weight conjugates in all brain regions. Immunoprecipitation of SUMOylated proteins from total brain extract and proteomic analysis revealed ~95 candidate proteins from a variety of functional classes, including a number of synaptic and cytoskeletal proteins. SUMO1 modification of synaptotagmin-1 was found to be elevated as compared to non-transgenic mice. This observation was associated with an age-dependent reduction in basal synaptic transmission and impaired presynaptic function as shown by altered paired pulse facilitation, as well as a decrease in spine density. The changes in neuronal function and morphology were also associated with a specific impairment in learning and memory while other behavioral features remained unchanged. These findings point to a significant contribution of SUMO1 modification on neuronal function which may have implications for mechanisms involved in mental retardation and neurodegeneration. PMID:26022678
SUMO1 Affects Synaptic Function, Spine Density and Memory.
Matsuzaki, Shinsuke; Lee, Linda; Knock, Erin; Srikumar, Tharan; Sakurai, Mikako; Hazrati, Lili-Naz; Katayama, Taiichi; Staniszewski, Agnieszka; Raught, Brian; Arancio, Ottavio; Fraser, Paul E
2015-01-01
Small ubiquitin-like modifier-1 (SUMO1) plays a number of roles in cellular events and recent evidence has given momentum for its contributions to neuronal development and function. Here, we have generated a SUMO1 transgenic mouse model with exclusive overexpression in neurons in an effort to identify in vivo conjugation targets and the functional consequences of their SUMOylation. A high-expressing line was examined which displayed elevated levels of mono-SUMO1 and increased high molecular weight conjugates in all brain regions. Immunoprecipitation of SUMOylated proteins from total brain extract and proteomic analysis revealed ~95 candidate proteins from a variety of functional classes, including a number of synaptic and cytoskeletal proteins. SUMO1 modification of synaptotagmin-1 was found to be elevated as compared to non-transgenic mice. This observation was associated with an age-dependent reduction in basal synaptic transmission and impaired presynaptic function as shown by altered paired pulse facilitation, as well as a decrease in spine density. The changes in neuronal function and morphology were also associated with a specific impairment in learning and memory while other behavioral features remained unchanged. These findings point to a significant contribution of SUMO1 modification on neuronal function which may have implications for mechanisms involved in mental retardation and neurodegeneration. PMID:26022678
The performance of semilocal and hybrid density functionals in 3d transition-metal chemistry
NASA Astrophysics Data System (ADS)
Furche, Filipp; Perdew, John P.
2006-01-01
We investigate the performance of contemporary semilocal and hybrid density functionals for bond energetics, structures, dipole moments, and harmonic frequencies of 3d transition-metal (TM) compounds by comparison with gas-phase experiments. Special attention is given to the nonempirical metageneralized gradient approximation (meta-GGA) of Tao, Perdew, Staroverov, and Scuseria (TPSS) [Phys. Rev. Lett. 91, 146401 (2003)], which has been implemented in TURBOMOLE for the present work. Trends and error patterns for classes of homologous compounds are analyzed, including dimers, monohydrides, mononitrides, monoxides, monofluorides, polyatomic oxides and halogenides, carbonyls, and complexes with organic π ligands such as benzene and cyclopentadienyl. Weakly bound systems such as Ca2, Mn2, and Zn2 are discussed. We propose a reference set of reaction energies for benchmark purposes. Our all-electron results with quadruple zeta valence basis sets validate semilocal density-functional theory as the workhorse of computational TM chemistry. Typical errors in bond energies are substantially larger than in (organic) main group chemistry, however. The Becke-Perdew'86 [Phys. Rev. A 38, 3098 (1988); Phys. Rev. B 33, 8822 (1986)] GGA and the TPSS meta-GGA have the best price/performance ratio, while the TPSS hybrid functional achieves a slightly lower mean absolute error in bond energies. The popular Becke three-parameter hybrid B3LYP underbinds significantly and tends to overestimate bond distances; we give a possible explanation for this. We further show that hybrid mixing does not reduce the width of the error distribution on our reference set. The error of a functional for the s-d transfer energy of a TM atom does not predict its error for TM bond energies and bond lengths. For semilocal functionals, self-interaction error in one- and three-electron bonds appears to be a major source of error in TM reaction energies. Nevertheless, TPSS predicts the correct ground
Dynamic density functional theory with hydrodynamic interactions and fluctuations.
Donev, Aleksandar; Vanden-Eijnden, Eric
2014-06-21
We derive a closed equation for the empirical concentration of colloidal particles in the presence of both hydrodynamic and direct interactions. The ensemble average of our functional Langevin equation reproduces known deterministic Dynamic Density Functional Theory (DDFT) [M. Rex and H. Löwen, "Dynamical density functional theory with hydrodynamic interactions and colloids in unstable traps," Phys. Rev. Lett. 101(14), 148302 (2008)], and, at the same time, it also describes the microscopic fluctuations around the mean behavior. We suggest separating the ideal (non-interacting) contribution from additional corrections due to pairwise interactions. We find that, for an incompressible fluid and in the absence of direct interactions, the mean concentration follows Fick's law just as for uncorrelated walkers. At the same time, the nature of the stochastic terms in fluctuating DDFT is shown to be distinctly different for hydrodynamically-correlated and uncorrelated walkers. This leads to striking differences in the behavior of the fluctuations around Fick's law, even in the absence of pairwise interactions. We connect our own prior work [A. Donev, T. G. Fai, and E. Vanden-Eijnden, "A reversible mesoscopic model of diffusion in liquids: from giant fluctuations to Fick's law," J. Stat. Mech.: Theory Exp. (2014) P04004] on fluctuating hydrodynamics of diffusion in liquids to the DDFT literature, and demonstrate that the fluid cannot easily be eliminated from consideration if one wants to describe the collective diffusion in colloidal suspensions. PMID:24952531
Dynamic density functional theory with hydrodynamic interactions and fluctuations
NASA Astrophysics Data System (ADS)
Donev, Aleksandar; Vanden-Eijnden, Eric
2014-06-01
We derive a closed equation for the empirical concentration of colloidal particles in the presence of both hydrodynamic and direct interactions. The ensemble average of our functional Langevin equation reproduces known deterministic Dynamic Density Functional Theory (DDFT) [M. Rex and H. Löwen, "Dynamical density functional theory with hydrodynamic interactions and colloids in unstable traps," Phys. Rev. Lett. 101(14), 148302 (2008)], and, at the same time, it also describes the microscopic fluctuations around the mean behavior. We suggest separating the ideal (non-interacting) contribution from additional corrections due to pairwise interactions. We find that, for an incompressible fluid and in the absence of direct interactions, the mean concentration follows Fick's law just as for uncorrelated walkers. At the same time, the nature of the stochastic terms in fluctuating DDFT is shown to be distinctly different for hydrodynamically-correlated and uncorrelated walkers. This leads to striking differences in the behavior of the fluctuations around Fick's law, even in the absence of pairwise interactions. We connect our own prior work [A. Donev, T. G. Fai, and E. Vanden-Eijnden, "A reversible mesoscopic model of diffusion in liquids: from giant fluctuations to Fick's law," J. Stat. Mech.: Theory Exp. (2014) P04004] on fluctuating hydrodynamics of diffusion in liquids to the DDFT literature, and demonstrate that the fluid cannot easily be eliminated from consideration if one wants to describe the collective diffusion in colloidal suspensions.
Dynamic density functional theory with hydrodynamic interactions and fluctuations
Donev, Aleksandar Vanden-Eijnden, Eric
2014-06-21
We derive a closed equation for the empirical concentration of colloidal particles in the presence of both hydrodynamic and direct interactions. The ensemble average of our functional Langevin equation reproduces known deterministic Dynamic Density Functional Theory (DDFT) [M. Rex and H. Löwen, “Dynamical density functional theory with hydrodynamic interactions and colloids in unstable traps,” Phys. Rev. Lett. 101(14), 148302 (2008)], and, at the same time, it also describes the microscopic fluctuations around the mean behavior. We suggest separating the ideal (non-interacting) contribution from additional corrections due to pairwise interactions. We find that, for an incompressible fluid and in the absence of direct interactions, the mean concentration follows Fick's law just as for uncorrelated walkers. At the same time, the nature of the stochastic terms in fluctuating DDFT is shown to be distinctly different for hydrodynamically-correlated and uncorrelated walkers. This leads to striking differences in the behavior of the fluctuations around Fick's law, even in the absence of pairwise interactions. We connect our own prior work [A. Donev, T. G. Fai, and E. Vanden-Eijnden, “A reversible mesoscopic model of diffusion in liquids: from giant fluctuations to Fick's law,” J. Stat. Mech.: Theory Exp. (2014) P04004] on fluctuating hydrodynamics of diffusion in liquids to the DDFT literature, and demonstrate that the fluid cannot easily be eliminated from consideration if one wants to describe the collective diffusion in colloidal suspensions.
Graphene oxide and adsorption of chloroform: A density functional study
NASA Astrophysics Data System (ADS)
Kuisma, Elena; Hansson, C. Fredrik; Lindberg, Th. Benjamin; Gillberg, Christoffer A.; Idh, Sebastian; Schröder, Elsebeth
2016-05-01
Chlorinated hydrocarbon compounds are of environmental concerns, since they are toxic to humans and other mammals, and are widespread, and exposure is hard to avoid. Understanding and improving methods to reduce the amount of the substances are important. We present an atomic-scale calculational study of the adsorption of chlorine-based substance chloroform (CHCl3) on graphene oxide, as a step in estimating the capacity of graphene oxide for filtering out such substances, e.g., from drinking water. The calculations are based on density functional theory, and the recently developed consistent-exchange functional for the van der Waals density-functional method is employed. We obtain values of the chloroform adsorption energy varying from roughly 0.2 to 0.4 eV per molecule. This is comparable to previously found results for chloroform adsorbed directly on clean graphene, using similar calculations. In a wet environment, like filters for drinking water, the graphene will not stay clean and will likely oxidize, and thus adsorption onto graphene oxide, rather than clean graphene, is a more relevant process to study.
Graphene oxide and adsorption of chloroform: A density functional study.
Kuisma, Elena; Hansson, C Fredrik; Lindberg, Th Benjamin; Gillberg, Christoffer A; Idh, Sebastian; Schröder, Elsebeth
2016-05-14
Chlorinated hydrocarbon compounds are of environmental concerns, since they are toxic to humans and other mammals, and are widespread, and exposure is hard to avoid. Understanding and improving methods to reduce the amount of the substances are important. We present an atomic-scale calculational study of the adsorption of chlorine-based substance chloroform (CHCl3) on graphene oxide, as a step in estimating the capacity of graphene oxide for filtering out such substances, e.g., from drinking water. The calculations are based on density functional theory, and the recently developed consistent-exchange functional for the van der Waals density-functional method is employed. We obtain values of the chloroform adsorption energy varying from roughly 0.2 to 0.4 eV per molecule. This is comparable to previously found results for chloroform adsorbed directly on clean graphene, using similar calculations. In a wet environment, like filters for drinking water, the graphene will not stay clean and will likely oxidize, and thus adsorption onto graphene oxide, rather than clean graphene, is a more relevant process to study. PMID:27179497
Relativistic cosmology number densities and the luminosity function
NASA Astrophysics Data System (ADS)
Iribarrem, A. S.; Lopes, A. R.; Ribeiro, M. B.; Stoeger, W. R.
2012-03-01
Aims: This paper studies the connection between the relativistic number density of galaxies down the past light cone in a Friedmann-Lemaître-Robertson-Walker spacetime with non-vanishing cosmological constant and the galaxy luminosity function (LF) data. It extends the redshift range of previous results presented in Albani et al. (2007, ApJ, 657, 760), where the galaxy distribution was studied out to z = 1. Observational inhomogeneities were detected at this range. This research also searches for LF evolution in the context of the framework advanced by Ribeiro and Stoeger (2003, ApJ, 592, 1), further developing the theory linking relativistic cosmology theory and LF data. Methods: Selection functions are obtained using the Schechter parameters and redshift parametrization of the galaxy LF obtained from an I-band selected dataset of the FORS deep field galaxy survey in the redshift range 0.5 ≤ z ≤ 5.0 for its blue bands and 0.75 ≤ z ≤ 3.0 for its red ones. Differential number counts, densities and other related observables are obtained, and then used with the calculated selection functions to study the empirical radial distribution of the galaxies in a fully relativistic framework. Results: The redshift range of the dataset used in this work, which is up to five times larger than the one used in previous studies, shows an increased relevance of the relativistic effects of expansion when compared to the evolution of the LF at the higher redshifts. The results also agree with the preliminary ones presented in Albani et al., suggesting a power-law behavior of relativistic densities at high redshifts when they are defined in terms of the luminosity distance.
Nuclear clustering in the energy density functional approach
Ebran, J.-P.; Khan, E.; Nikšić, T.; Vretenar, D.
2015-10-15
Nuclear Energy Density Functionals (EDFs) are a microscopic tool of choice extensively used over the whole chart to successfully describe the properties of atomic nuclei ensuing from their quantum liquid nature. In the last decade, they also have proved their ability to deal with the cluster phenomenon, shedding a new light on its fundamental understanding by treating on an equal footing both quantum liquid and cluster aspects of nuclei. Such a unified microscopic description based on nucleonic degrees of freedom enables to tackle the question pertaining to the origin of the cluster phenomenon and emphasizes intrinsic mechanisms leading to the emergence of clusters in nuclei.
Application of Density Functional Theory to Systems Containing Metal Atoms
NASA Technical Reports Server (NTRS)
Bauschlicher, Charles W., Jr.; Arnold, James O. (Technical Monitor)
1997-01-01
The accuracy of density functional theory (DFT) for problems involving metal atoms is considered. The DFT results are compared with experiment as well as results obtained using the coupled cluster approach. The comparisons include geometries, frequencies, and bond energies. The systems considered include MO2, M(OH)+(sub n), MNO+, and MCO+(sub 2). The DFT works well for frequencies and geometries, even in cases with symmetry breaking; however, some examples have been found where the symmetry breaking is quite severe and the DFT methods do not work well. The calculation of bond energies is more difficult and examples of the successes as well as failures of DFT will be given.
Quantification of Uncertainties in Nuclear Density Functional Theory
Schunck, N.; McDonnell, J.D.; Higdon, D.; Sarich, J.; Wild, S.
2015-01-15
Reliable predictions of nuclear properties are needed as much to answer fundamental science questions as in applications such as reactor physics or data evaluation. Nuclear density functional theory is currently the only microscopic, global approach to nuclear structure that is applicable throughout the nuclear chart. In the past few years, a lot of effort has been devoted to setting up a general methodology to assess theoretical uncertainties in nuclear DFT calculations. In this paper, we summarize some of the recent progress in this direction. Most of the new material discussed here will be be published in separate articles.
Application of Density Functional Theory to Systems Containing Metal Atoms
NASA Technical Reports Server (NTRS)
Bauschlicher, Charles W., Jr.
2006-01-01
The accuracy of density functional theory (DFT) for problems involving metal atoms is considered. The DFT results are compared with experiment as well as results obtained using the coupled cluster approach. The comparisons include geometries, frequencies, and bond energies. The systems considered include MO2, M(OH)+n, MNO+, and MCO+2. The DFT works well for frequencies and geometries, even in case with symmetry breaking; however, some examples have been found where the symmetry breaking is quite severe and the DFT methods do not work well. The calculation of bond energies is more difficult and examples of successes as well as failures of DFT will be given.
Momentum distribution function of the electron gas at metallic densities
NASA Astrophysics Data System (ADS)
Takada, Yasutami; Yasuhara, H.
1991-10-01
The momentum distribution function n(k) of the electron gas is calculated in the effective-potential-expansion method at metallic densities. The recently established self-consistency relation between n(k) and the correlation energy [Y. Takada and T. Kita, J. Phys. Soc. Jpn. 60, 25 (1991)] is employed to check the accuracy of our results. This check shows that the effective-potential-expansion method provides probably the exact and at least more accurate results of n(k) than all the other methods that have given n(k) thus far.
Density functional study of the cysteine adsorption on Au nanoclusters
NASA Astrophysics Data System (ADS)
Pérez, L. A.; López-Lozano, X.; Garzón, I. L.
2009-04-01
The adsorption of the cysteine amino acid (H-SCβH2-CαH-NH2-COOH) on the Au55 cluster is investigated through density functional theory calculations. Two isomers, with icosahedral (Ih) and chiral (C1) geometries, of the Au55 cluster are used to calculate the adsorption energy of the cysteine on different facets of these isomers. Results, only involving the S(thiolate)-Au bonding show that the higher adsorption energies are obtained when the sulfur atom is bonded to an asymmetrical bridge site at the facet containing Au atoms with the lowest coordination of the C1 cluster isomer.
Nuclear clustering in the energy density functional approach
NASA Astrophysics Data System (ADS)
Ebran, J.-P.; Khan, E.; Nikšić, T.; Vretenar, D.
2015-10-01
Nuclear Energy Density Functionals (EDFs) are a microscopic tool of choice extensively used over the whole chart to successfully describe the properties of atomic nuclei ensuing from their quantum liquid nature. In the last decade, they also have proved their ability to deal with the cluster phenomenon, shedding a new light on its fundamental understanding by treating on an equal footing both quantum liquid and cluster aspects of nuclei. Such a unified microscopic description based on nucleonic degrees of freedom enables to tackle the question pertaining to the origin of the cluster phenomenon and emphasizes intrinsic mechanisms leading to the emergence of clusters in nuclei.
Density functional theory for strongly-correlated ultracold dipolar gases
NASA Astrophysics Data System (ADS)
Malet Giralt, Francesc; Reimann, Stephanie; Gori-Giorgi, Paola; Lund University Collaboration
2014-03-01
We address quasi-one-dimensional strongly-correlated dipolar ultracold gases by means of density functional theory. We make use of an approximation for the Hartree-exchange-correlation that has been shown to be very accurate for electronic systems with coulombic interactions. We show that this approach allows to treat systems with very large particle numbers at relatively low computational cost. This work has been supported by a VIDI grant of the NWO and a Marie Curie grant within the FP7 programme.
Density Functional Study of the structural properties in Tamoxifen
NASA Astrophysics Data System (ADS)
de Coss-Martinez, Romeo; Tapia, Jorge A.; Quijano-Quiñones, Ramiro F.; Canto, Gabriel I.
2013-03-01
Using the density functional theory, we have studied the structural properties of Tamoxifen. The calculations were performed with two methodological approaches, which were implemented in SIESTA and Spartan codes. For SIESTA, we considerate a linear combination of atomic orbitals method, using pseudopotentials and the van der Waals approximation for the exchange-correlation potential. Here we analyzed and compared the atomic structure between our results and other theoretical study. We found differences in the bond lengths between the results, that could be attributed to code approaches in each one. This work was supported under Grant FOMIX 2011-09 N: 170297 of Ph.D. A. Tapia.
Determining Ionospheric Irregularity Spectral Density Function from Japan GEONET
NASA Astrophysics Data System (ADS)
Lay, E. H.; Light, M. E.; Parker, P. A.; Carrano, C. S.; Haaser, R. A.
2015-12-01
Japan's GEONET GPS network is the densest GPS monitoring network in the world, with 1200+ receivers over the area of Japan. Measuring and calibrating the integrated total electron content (TEC) from each station has been done in many cases to provide detailed maps of ionospheric disturbances over Japan. We use TEC measurements from Japan's GEONET array to determine an empirically derived description of the 2-dimensional scale sizes of spatial irregularities above Japan. The contributions from various scale sizes will be included in a statistical description for the irregularity spectral density (ISD) function. We will compare the statistics of the spatial irregularities between calm and moderately scintillated conditions.
Density functional theory calculations of Rh-β-diketonato complexes.
Conradie, J
2015-01-28
Density functional theory (DFT) results on the geometry, energies and charges of selected Rh-β-diketonato reactants, products and transition states are discussed. Various DFT techniques are used to increase our understanding of the orientation of ligands coordinated to Rh, to identify the lowest energy geometry of possible geometrical isomers and to get a molecular orbital understanding of ground and transition states. Trends and relationships obtained between DFT calculated energies and charges, experimentally measured values and electronic parameters describing the electron donating power of groups and ligands, enable the design of ligands and complexes of specific reactivity. PMID:25429658
Relativistic Energy Density Functionals: Exotic modes of excitation
Vretenar, D.; Paar, N.; Marketin, T.
2008-11-11
The framework of relativistic energy density functionals has been applied to the description of a variety of nuclear structure phenomena, not only in spherical and deformed nuclei along the valley of {beta}-stability, but also in exotic systems with extreme isospin values and close to the particle drip-lines. Dynamical aspects of exotic nuclear structure have been investigated with the relativistic quasiparticle random-phase approximation. We present results for the evolution of low-lying dipole (pygmy) strength in neutron-rich nuclei, and charged-current neutrino-nucleus cross sections.
DENSITY-FUNCTIONAL STUDY OF Zr-BASED ACTINIDE ALLOYS
Landa, A; Soderlind, P; Turchi, P; Vitos, L; Ruban, A
2008-06-26
Density-functional formalism is applied to study the phase equilibria in the U-Zr system. The obtained ground-state properties of the {gamma} (bcc) and {delta} (C32) phases are in good agreement with experimental data. The decomposition curve for the {gamma}-based U-Zr solutions is calculated. We argue that stabilization of the {delta}-UZr{sub 2} phase relative to the {alpha}-Zr (hcp) structure is due to an increase of the Zr d-band occupancy that occurs when U is alloyed with Zr.
Strained graphene: tight-binding and density functional calculations
NASA Astrophysics Data System (ADS)
Ribeiro, R. M.; Pereira, Vitor M.; Peres, N. M. R.; Briddon, P. R.; Castro Neto, A. H.
2009-11-01
We determine the band structure of graphene under strain using density functional calculations. The ab initio band structure is then used to extract the best fit to the tight-binding hopping parameters used in a recent microscopic model of strained graphene. It is found that the hopping parameters may increase or decrease upon increasing strain, depending on the orientation of the applied stress. The fitted values are compared with an available parameterization for the dependence of the orbital overlap on the distance separating the two carbon atoms. It is also found that strain does not induce a gap in graphene, at least for deformations up to 10%.
Garcia-Aldea, David; Alvarellos, J. E.
2008-02-15
We propose a kinetic energy density functional scheme with nonlocal terms based on the von Weizsaecker functional, instead of the more traditional approach where the nonlocal terms have the structure of the Thomas-Fermi functional. The proposed functionals recover the exact kinetic energy and reproduce the linear response function of homogeneous electron systems. In order to assess their quality, we have tested the total kinetic energies as well as the kinetic energy density for atoms. The results show that these nonlocal functionals give as good results as the most sophisticated functionals in the literature. The proposed scheme for constructing the functionals means a step ahead in the field of fully nonlocal kinetic energy functionals, because they are capable of giving better local behavior than the semilocal functionals, yielding at the same time accurate results for total kinetic energies. Moreover, the functionals enjoy the possibility of being evaluated as a single integral in momentum space if an adequate reference density is defined, and then quasilinear scaling for the computational cost can be achieved.
Analysis of the local-density approximation of density-functional theory
NASA Astrophysics Data System (ADS)
Sahni, Viraht; Bohnen, K.-P.; Harbola, Manoj K.
1988-03-01
In this paper we perform a configuration-space analysis of the local-density approximation (LDA) for the exchange-correlation energy functional of Kohn-Sham density-functional theory in terms of the corresponding average exchange-correlation charge (hole) and energy densities. According to our analysis, the explanation for the quantitative success of the LDA based on the hole charge-conservation sum rule and the assumed consequent cancellation of errors in the spherical averages of the hole is inadequate. The principal conclusion of our work is that the constraint of charge neutrality is a necessary but not sufficient condition for an approximate energy functional to lead to accurate ground-state energies and ionization potentials. The significant additional requirement for the functional is that it must, at least qualitatively, reproduce correctly the structure of the hole as a function of electron position. We perform our calculations within the exchange-only approximation as applied to atoms and jellium metal surfaces. In atoms the Fermi hole is localized about the nucleus; as a consequence the LDA Fermi hole is accurate only for electron positions close to it. However, we show that the spherically averaged LDA hole is accurate for electron positions in the shell regions; it is substantially in error in the intershell and classically forbidden regions. The fact that the principal contribution to the exchange energy comes from the inner-shell region of the atom, where the LDA hole is accurate, explains why the errors in the LDA ground-state energies are small. However, the ionization potential, which depends on the structure of the hole in the outer regions of the atom, is substantially in error in the LDA since here the LDA hole differs significantly from the exact one. For metallic surfaces, on the other hand, as an electron is pulled from within the metal to infinity outside, the Fermi hole is delocalized and spread throughout the crystal. As a consequence
Lu, Qi Liang; Luo, Qi Quan; Huang, Shou Guo; Li, Yi De; Wan, Jian Guo
2016-07-01
An optimization strategy combining global semiempirical quantum mechanical search with all-electron density functional theory was adopted to determine the lowest energy structure of (GaSb)n clusters up to n = 9. The growth pattern of the clusters differed from those of previously reported group III-V binary clusters. A cagelike configuration was found for cluster sizes n ≤ 7. The structure of (GaSb)6 deviated from that of other III-V clusters. Competition existed between core-shell and hollow cage structures of (GaSb)7. Novel noncagelike structures were energetically preferred over the cages for the (GaSb)8 and (GaSb)9 clusters. Electronic properties, such as vertical ionization potential, adiabatic electron affinities, HOMO-LUMO gaps, and average on-site charges on Ga or Sb atoms, as well as binding energies, were computed. PMID:27322830
Lithium adsorption on graphite from density functional theory calculations.
Valencia, Felipe; Romero, Aldo H; Ancilotto, Francesco; Silvestrelli, Pier Luigi
2006-08-01
The structural, energetic, and electronic properties of the Li/graphite system are studied through density functional theory (DFT) calculations using both the local spin density approximation (LSDA), and the gradient-corrected Perdew-Burke-Ernzerhof (PBE) approximation to the exchange-correlation energy. The calculations were performed using plane waves basis, and the electron-core interactions are described using pseudopotentials. We consider a disperse phase of the adsorbate comprising one Li atom for each 16 graphite surface cells, in a slab geometry. The close contact between the Li nucleus and the graphene plane results in a relatively large binding energy (larger than 1.1 eV). A detailed analysis of the electronic charge distribution, density difference distribution, and band structures indicates that one valence electron is entirely transferred from the atom to the surface, which gives rise to a strong interaction between the resulting lithium ion and the cloud of pi electrons in the substrate. We show that it is possible to explain the differences in the binding of Li, Na, and K adatoms on graphite considering the properties of the corresponding cation/aromatic complexes. PMID:16869593
Constrained Density Functional Theory by Imaginary Time-Step Method
NASA Astrophysics Data System (ADS)
Kidd, Daniel
Constrained Density Functional Theory (CDFT) has been a popular choice within the last decade for sidestepping the self interaction problem within long-range charge transfer calculations. Typically an inner constraint loop is added within the self-consistent field iterations of DFT in order to enforce this charge transfer state by means of a Lagrange multiplier method. In this work, an alternate implementation of CDFT is introduced, that of the imaginary time-step method, which lends itself more readily to real space calculations in the ability to solve numerically for 3D local external potentials which enforce arbitrary given densities. This method has been shown to reproduce the proper 1 / R dependence of charge transfer systems in real space calculations as well as the ability to generate useful constraint potentials. As an example application, this method is shown to be capable of describing defects within periodic systems using finite calculations by constraining the 3D density to that of the periodically calculated perfect system at the boundaries.
Antisites in III-V semiconductors: Density functional theory calculations
NASA Astrophysics Data System (ADS)
Chroneos, A.; Tahini, H. A.; Schwingenschlögl, U.; Grimes, R. W.
2014-07-01
Density functional based simulation, corrected for finite size effects, is used to investigate systematically the formation of antisite defects in III-V semiconductors (III = Al, Ga, and In and V = P, As, and Sb). Different charge states are modelled as a function of the Fermi level and under different growth conditions. The formation energies of group III antisites ( III V q) decrease with increasing covalent radius of the group V atom though not group III radius, whereas group V antisites ( V I I I q) show a consistent decrease in formation energies with increase in group III and group V covalent radii. In general, III V q defects dominate under III-rich conditions and V I I I q under V-rich conditions. Comparison with equivalent vacancy formation energy simulations shows that while antisite concentrations are always dominant under stoichiometric conditions, modest variation in growth or doping conditions can lead to a significantly higher concentration of vacancies.
A numerical efficient way to minimize classical density functional theory
NASA Astrophysics Data System (ADS)
Edelmann, Markus; Roth, Roland
2016-02-01
The minimization of the functional of the grand potential within the framework of classical density functional theory in three spatial dimensions can be numerically very demanding. The Picard iteration, that is often employed, is very simple and robust but can be rather slow. While a number of different algorithms for optimization problems have been suggested, there is still great need for additional strategies. Here, we present an approach based on the limited memory Broyden algorithm that is efficient and relatively simple to implement. We demonstrate the performance of this algorithm with the minimization of an inhomogeneous bulk structure of a fluid with competing interactions. For the problems we studied, we find that the presented algorithm improves performance by roughly a factor of three.
Computational predictions of energy materials using density functional theory
NASA Astrophysics Data System (ADS)
Jain, Anubhav; Shin, Yongwoo; Persson, Kristin A.
2016-01-01
In the search for new functional materials, quantum mechanics is an exciting starting point. The fundamental laws that govern the behaviour of electrons have the possibility, at the other end of the scale, to predict the performance of a material for a targeted application. In some cases, this is achievable using density functional theory (DFT). In this Review, we highlight DFT studies predicting energy-related materials that were subsequently confirmed experimentally. The attributes and limitations of DFT for the computational design of materials for lithium-ion batteries, hydrogen production and storage materials, superconductors, photovoltaics and thermoelectric materials are discussed. In the future, we expect that the accuracy of DFT-based methods will continue to improve and that growth in computing power will enable millions of materials to be virtually screened for specific applications. Thus, these examples represent a first glimpse of what may become a routine and integral step in materials discovery.
Density functional theory an effective method to model polythiophenes
NASA Astrophysics Data System (ADS)
Venkateswaran, S.
The luminescent polymer, poly[2-(3-thienyl)ethanol butoxycarbonyl-methyl urethane, called popularly as PURET, has rekindled research interests due to the recent discovery of its ability for detection of explosives at trace levels of molecules in their vapor phase. In this computational study, Hartree-Fock and/or Density Functional Theory (DFT) methods are applied, using Gaussian09 W software, for calculating the HOMO-LUMO energy levels, the Dipole Moment, and the UV-Vis and IR spectra for the Oligomers of PURET monomer, dimer, and trimer. Similar calculations for a few other Thiophene derivatives, such as TAA. TMA, 3HT, and TTZ, are also shown. DFT-based calculations, employing especially the B3LYP functional, are shown to systematically converge to experimental levels of accuracy for PURET Oligomers.
Density functional theory study of rutile VO2 surfaces
NASA Astrophysics Data System (ADS)
Mellan, Thomas A.; Grau-Crespo, Ricardo
2012-10-01
We present the results of a density functional theory investigation of the surfaces of rutile-like vanadium dioxide, VO2(R). We calculate the surface energies of low Miller index planes and find that the most stable surface orientation is the (110). The equilibrium morphology of a VO2(R) particle has an acicular shape, laterally confined by (110) planes and topped by (011) planes. The redox properties of the (110) surface are investigated by calculating the relative surface free energies of the non-stoichiometric compositions as a function of oxygen chemical potential. It is found that the VO2(110) surface is oxidized with respect to the stoichiometric composition, not only at ambient conditions but also at the more reducing conditions under which bulk VO2 is stable in comparison with bulk V2O5. The adsorbed oxygen forms surface vanadyl species much more favorably than surface peroxo species.
Towards the island of stability with relativistic energy density functionals
Prassa, V.; Niksic, T.; Lalazissis, G. A.; Vretenar, D.
2012-10-20
Relativistic energy density functionals (REDF) provide a complete and accurate, global description of nuclear structure phenomena. Modern semi-empirical functionals, adjusted to the nuclear matter equation of state and to empirical masses of deformed nuclei, are applied to studies of shapes of superheavy nuclei. The theoretical framework is tested in a comparison to empirical masses, quadrupole deformations, and energy barriers of actinide nuclei. The model is used in a self-consistent mean-field calculation of spherical, axial and triaxial shapes of superheavy nuclei, alpha-decay energies and lifetimes. The effect of explicit treatment of collective correlations is analyzed in calculations that consistently use a collective Hamiltonian model based on REDFs.
Electronic properties of graphene nanoribbons: A density functional investigation
Kumar, Sandeep Sharma, Hitesh
2015-05-15
Density functional theory calculations have been performed on graphene nano ribbons (GNRs) to investigate the electronic properties as a function of chirality, size and hydrogenation on the edges. The calculations were performed on GNRs with armchair and zigzag configurations with 28, 34, 36, 40, 50, 56, 62, 66 carbon atoms. The structural stability of AGNR and ZGNR increases with the size of nanoribbon where as hydrogenation of GNR tends to lowers their structural stability. All GNRs considered have shown semiconducting behavior with HOMO-LUMO gap decreasing with the increase in the GNR size. The hydrogenation of GNR decreases its HOMO-LUMO gap significantly. The results are in agreement with the available experimental and theoretical results.
Uncertainty Quantification and Propagation in Nuclear Density Functional Theory
Schunck, N; McDonnell, J D; Higdon, D; Sarich, J; Wild, S M
2015-03-17
Nuclear density functional theory (DFT) is one of the main theoretical tools used to study the properties of heavy and superheavy elements, or to describe the structure of nuclei far from stability. While on-going eff orts seek to better root nuclear DFT in the theory of nuclear forces, energy functionals remain semi-phenomenological constructions that depend on a set of parameters adjusted to experimental data in fi nite nuclei. In this paper, we review recent eff orts to quantify the related uncertainties, and propagate them to model predictions. In particular, we cover the topics of parameter estimation for inverse problems, statistical analysis of model uncertainties and Bayesian inference methods. Illustrative examples are taken from the literature.
BUILDING A UNIVERSAL NUCLEAR ENERGY DENSITY FUNCTIONAL (UNEDF)
Nazarewicz, Witold
2012-07-01
The long-term vision initiated with UNEDF is to arrive at a comprehensive, quantitative, and unified description of nuclei and their reactions, grounded in the fundamental interactions between the constituent nucleons. We seek to replace current phenomenological models of nuclear structure and reactions with a well-founded microscopic theory that delivers maximum predictive power with well-quantified uncertainties. Specifically, the mission of this project has been three-fold: First, to find an optimal energy density functional (EDF) using all our knowledge of the nucleonic Hamiltonian and basic nuclear properties. Second, to apply the EDF theory and its extensions to validate the functional using all the available relevant nuclear structure and reaction data. Third, to apply the validated theory to properties of interest that cannot be measured, in particular the properties needed for reaction theory.
Hybrid Density Functionals Tuned towards Fulfillment of Fundamental DFT Conditions
NASA Astrophysics Data System (ADS)
Scheffler, Matthias
2014-03-01
Hybrid exchange-correlation functionals (XC), e.g. PBE0 and HSE, have significantly improved the theoretical description of molecules and solids. Their degree of exact-exchange admixture (α) is in principle a functional of the electron density, but the functional form is not known. In this talk, I will discuss fundamental conditions of exact density-functional theory (DFT) that enable us to find the optimal choice of α for ground-state calculations. In particular, I will discuss the fact that the highest occupied Kohn-Sham level of an N-electron system (ɛHOMO(N)) should be constant for fractional particle numbers between N and N-1 and equals the ionization potential (IP), as given by the total-energy difference. In practice, we realize this in three different ways. XC(α) will be optimized (opt-XC) until it (i) fulfills the condition: ɛHOMO(N) =ɛHOMO (N-1/2) or the Kohn-Sham HOMO agrees with the ionization potential computed in a more sophisticated approach ɛHOMO(N) = IP such as (ii) the G0W0 @opt-XC method or (iii) CCSD(T) or full CI. Using such an opt-XC is essential for describing electron transfer between (organic) molecules, as exemplified by the TTF/TCNQ dimer. It also yields vertical ionization energies of the G2 test set of quantum chemistry with a mean absolute percentage error of only ~3%. Furthermore, our approach removes the starting-point uncertainty of GW calculations and thus bears some resemblance to the consistent starting point scheme and quasiparticle self-consistent GW. While our opt-XC approach yields large α values for small molecules in the gas phase, we find that α needs to be 0.25 or less for organic molecules adsorbed on metals. Work performed in collaboration with V. Atalla, N.A. Richter, S.V. Levchenko, and P. Rinke
Hydroxyl functionalized thermosensitive microgels with quadratic crosslinking density distribution.
Elmas, Begum; Tuncel, Murvet; Senel, Serap; Patir, S; Tuncel, Ali
2007-09-01
N-isopropylacrylamide (NIPA) based uniform thermosensitive microgels were synthesized by dispersion polymerization by using relatively hydrophilic crosslinking agents with hydroxyl functionality. Glycerol dimethacrylate (GDMA), pentaerythritol triacrylate (PETA) and pentaerythritol propoxylate triacrylate (PEPTA) were used as crosslinking agents with different hydrophilicities. A protocol was first proposed to determine the crosslinking density distribution in the thermosensitive microgel particles by confocal laser scanning microscopy (CLSM). The microgels were fluorescently labeled by using hydroxyl group of the crosslinking agent. The CLSM observations performed with the microgels synthesized by three different crosslinking agents showed that the crosslinking density exhibited a quadratic decrease with the increasing radial distance in the spherical microgel particles. This structure led to the formation of more loose gel structure on the particle surface with respect to the center. Then the use of hydrophilic crosslinking agents in the dispersion polymerization of NIPA made possible the synthesis of thermosensitive microgels carrying long, flexible and chemically derivatizable (i.e., hydroxyl functionalized) fringes on the surface by a single-stage dispersion polymerization. The microgels with all crosslinking agents exhibited volume phase transition with the increasing temperature. The microgel obtained by the most hydrophilic crosslinking agent, GDMA exhibited higher hydrodynamic diameters in the fully swollen form at low temperatures than those obtained by PETA and PEPTA. Higher hydrodynamic size decrease from fully swollen form to the fully shrunken form was also observed with the same microgel. PMID:17532327
Probability density function transformation using seeded localized averaging
Dimitrov, N. B.; Jordanov, V. T.
2011-07-01
Seeded Localized Averaging (SLA) is a spectrum acquisition method that averages pulse-heights in dynamic windows. SLA sharpens peaks in the acquired spectra. This work investigates the transformation of the original probability density function (PDF) in the process of applying SLA procedure. We derive an analytical expression for the resulting probability density function after an application of SLA. In addition, we prove the following properties: 1) for symmetric distributions, SLA preserves both the mean and symmetry. 2) for uni-modal symmetric distributions, SLA reduces variance, sharpening the distributions peak. Our results are the first to prove these properties, reinforcing past experimental observations. Specifically, our results imply that in the typical case of a spectral peak with Gaussian PDF the full width at half maximum (FWHM) of the transformed peak becomes narrower even with averaging of only two pulse-heights. While the Gaussian shape is no longer preserved, our results include an analytical expression for the resulting distribution. Examples of the transformation of other PDFs are presented. (authors)
Density functional study of silver defects in telluride thermoelectric materials
NASA Astrophysics Data System (ADS)
Ryu, Byungki; Oh, Min-Wook; Park, Su-Dong
2015-03-01
Silver impurity in telluride thermoelectric materials forms various defect and impurity structures, such as AgSb rich nanoregion in Ag-Sb-Pb-Te, Ag2Te and metallic silver in PbTe. To understand the atomic, electronic, energetic, and diffusion properties of silver impurities in telluride systems, we have performed the density functional theory and density functional perturbation theory calculations of silver doped PbTe. Under Te and Ag rich condition, silver telluride impurity phase or Ag-dimer defects are expected to be easily formed. Under Te poor condition, silver point defects are calculated to be easily formed and they are more stable than native point defects of PbTe, implying that silver point defect might be the major dopant responsible for the carrier generation in PbTe. We also calculated the diffusion coefficient and diffusion length of silver point defect in PbTe. Based on the results, we discussed the electrical and thermoelectric properties of silver doped PbTe. This work was supported by the National Institute of Supercomputing and Network/Korea Institute of Science and Technology Information with supercomputing resources including technical support (KSC-2014-C1-022).
Direct Neutron Capture Calculations with Covariant Density Functional Theory Inputs
NASA Astrophysics Data System (ADS)
Zhang, Shi-Sheng; Peng, Jin-Peng; Smith, Michael S.; Arbanas, Goran; Kozub, Ray L.
2014-09-01
Predictions of direct neutron capture are of vital importance for simulations of nucleosynthesis in supernovae, merging neutron stars, and other astrophysical environments. We calculate the direct capture cross sections for E1 transitions using nuclear structure information from a covariant density functional theory as input for the FRESCO coupled-channels reaction code. We find good agreement of our predictions with experimental cross section data on the double closed-shell targets 16O, 48Ca, and 90Zr, and the exotic nucleus 36S. Extensions of the technique for unstable nuclei and for large-scale calculations will be discussed. Predictions of direct neutron capture are of vital importance for simulations of nucleosynthesis in supernovae, merging neutron stars, and other astrophysical environments. We calculate the direct capture cross sections for E1 transitions using nuclear structure information from a covariant density functional theory as input for the FRESCO coupled-channels reaction code. We find good agreement of our predictions with experimental cross section data on the double closed-shell targets 16O, 48Ca, and 90Zr, and the exotic nucleus 36S. Extensions of the technique for unstable nuclei and for large-scale calculations will be discussed. Supported by the U.S. Dept. of Energy, Office of Nuclear Physics.
Towards simple orbital-dependent density functionals for molecular dissociation
NASA Astrophysics Data System (ADS)
Zhang, Igor Ying; Richter, Patrick; Scheffler, Matthias
2015-03-01
Density functional theory (DFT) is one of the leading first-principles electronic-structure theories. However, molecular dissociation remains a challenge, because it requires a well-balanced description of the drastically different electronic structure at different bond lengths. One typical and well-documented case is the dissociation of both H2+ and H2, for which all popular DFT functionals fail. We start from the Bethe-Goldstone equation to propose a simple orbital-dependent correlation functional which generalizes the linear adiabatic connection approach. The resulting scheme is based on second-order perturbation theory (PT2), but includes the self-consistent coupling of electron-hole pairs, which ensures the correct H2 dissociation limit and gives a finite correlation energy for systems with a (near)-degenerate energy gap. This coupling PT2-like (CPT2) approximation delivers a significant improvement over all existing functionals for both H2 and H2+ dissociation. We will demonstrate the reason for this improvement analytically for H2 in a minimal basis.
Medium density polyethylene composites with functionalized carbon nanotubes
NASA Astrophysics Data System (ADS)
Pulikkathara, Merlyn X.; Kuznetsov, Oleksandr V.; Peralta, Ivana R. G.; Wei, Xin; Khabashesku, Valery N.
2009-05-01
A strong interface between the single-walled carbon nanotubes (SWNTs) and polymer matrix is necessary to achieve enhanced mechanical properties of composites. In this work a series of sidewall-functionalized SWNTs have been investigated in order to evaluate the effect of functionalization on SWNT aspect ratio and composite interfacial chemistry and their role on mechanical properties of a medium density polyethylene (MDPE) matrix. Fluorinated nanotubes (F-SWNTs) were used as precursors for subsequent sidewall functionalization with long chain alkyl groups to produce an F-SWNT- C11H23 derivative. The latter was refluorinated to yield a new perfluorinated derivative, F-SWNT- C11FxHy. The functionalized SWNTs as well as the pristine SWNTs were integrated into an MDPE matrix at a 1 wt% loading. The nanotubes and composite materials were characterized with FTIR, Raman spectroscopy, NMR, XPS, AFM, SEM, TGA, DSC and tensile tests. When incorporated into polyethylene, the new perfluorinated derivative, F-SWNT- C11FxHy, yielded the highest tensile strength value among all nanotube/MDPE composite samples, showing a 52% enhancement in comparison with the neat MDPE. The 1 wt% SWNT/MDPE composite contained nanotubes with a larger aspect ratio but, due to a lack of interfacial chemistry, it resulted in less improvement in mechanical properties compared to the composites made with the fluorinated SWNT derivatives.
Medium density polyethylene composites with functionalized carbon nanotubes.
Pulikkathara, Merlyn X; Kuznetsov, Oleksandr V; Peralta, Ivana R G; Wei, Xin; Khabashesku, Valery N
2009-05-13
A strong interface between the single-walled carbon nanotubes (SWNTs) and polymer matrix is necessary to achieve enhanced mechanical properties of composites. In this work a series of sidewall-functionalized SWNTs have been investigated in order to evaluate the effect of functionalization on SWNT aspect ratio and composite interfacial chemistry and their role on mechanical properties of a medium density polyethylene (MDPE) matrix. Fluorinated nanotubes (F-SWNTs) were used as precursors for subsequent sidewall functionalization with long chain alkyl groups to produce an F-SWNT- C(11)H(23) derivative. The latter was refluorinated to yield a new perfluorinated derivative, F-SWNT- C(11)F(x)H(y). The functionalized SWNTs as well as the pristine SWNTs were integrated into an MDPE matrix at a 1 wt% loading. The nanotubes and composite materials were characterized with FTIR, Raman spectroscopy, NMR, XPS, AFM, SEM, TGA, DSC and tensile tests. When incorporated into polyethylene, the new perfluorinated derivative, F-SWNT- C(11)F(x)H(y), yielded the highest tensile strength value among all nanotube/MDPE composite samples, showing a 52% enhancement in comparison with the neat MDPE. The 1 wt% SWNT/MDPE composite contained nanotubes with a larger aspect ratio but, due to a lack of interfacial chemistry, it resulted in less improvement in mechanical properties compared to the composites made with the fluorinated SWNT derivatives. PMID:19420641
Abnormal Functional Connectivity Density in Post-traumatic Stress Disorder.
Zhang, Youxue; Xie, Bing; Chen, Heng; Li, Meiling; Liu, Feng; Chen, Huafu
2016-05-01
Post-traumatic stress disorder (PTSD) is a psychiatric disorder that occurs in individuals who have experienced life-threatening mental traumas. Previous neuroimaging studies have indicated that the pathology of PTSD may be associated with the abnormal functional integration among brain regions. In the current study, we used functional connectivity density (FCD) mapping, a novel voxel-wise data-driven approach based on graph theory, to explore aberrant FC through the resting-state functional magnetic resonance imaging of the PTSD. We calculated both short- and long-range FCD in PTSD patients and healthy controls (HCs). Compared with HCs, PTSD patients showed significantly increased long-range FCD in the left dorsolateral prefrontal cortex (DLPFC), but no abnormal short-range FCD was found in PTSD. Furthermore, seed-based FC analysis of the left DLPFC showed increased connectivity in the left superior parietal lobe and visual cortex of PTSD patients. The results suggested that PTSD patients experienced a disruption of intrinsic long-range functional connections in the fronto-parietal network and visual cortex, which are associated with attention control and visual information processing. PMID:26830769
Daubechies wavelets for linear scaling density functional theory.
Mohr, Stephan; Ratcliff, Laura E; Boulanger, Paul; Genovese, Luigi; Caliste, Damien; Deutsch, Thierry; Goedecker, Stefan
2014-05-28
We demonstrate that Daubechies wavelets can be used to construct a minimal set of optimized localized adaptively contracted basis functions in which the Kohn-Sham orbitals can be represented with an arbitrarily high, controllable precision. Ground state energies and the forces acting on the ions can be calculated in this basis with the same accuracy as if they were calculated directly in a Daubechies wavelets basis, provided that the amplitude of these adaptively contracted basis functions is sufficiently small on the surface of the localization region, which is guaranteed by the optimization procedure described in this work. This approach reduces the computational costs of density functional theory calculations, and can be combined with sparse matrix algebra to obtain linear scaling with respect to the number of electrons in the system. Calculations on systems of 10,000 atoms or more thus become feasible in a systematic basis set with moderate computational resources. Further computational savings can be achieved by exploiting the similarity of the adaptively contracted basis functions for closely related environments, e.g., in geometry optimizations or combined calculations of neutral and charged systems. PMID:24880269
Daubechies wavelets for linear scaling density functional theory
Mohr, Stephan; Ratcliff, Laura E.; Genovese, Luigi; Caliste, Damien; Deutsch, Thierry; Boulanger, Paul; Goedecker, Stefan
2014-05-28
We demonstrate that Daubechies wavelets can be used to construct a minimal set of optimized localized adaptively contracted basis functions in which the Kohn-Sham orbitals can be represented with an arbitrarily high, controllable precision. Ground state energies and the forces acting on the ions can be calculated in this basis with the same accuracy as if they were calculated directly in a Daubechies wavelets basis, provided that the amplitude of these adaptively contracted basis functions is sufficiently small on the surface of the localization region, which is guaranteed by the optimization procedure described in this work. This approach reduces the computational costs of density functional theory calculations, and can be combined with sparse matrix algebra to obtain linear scaling with respect to the number of electrons in the system. Calculations on systems of 10 000 atoms or more thus become feasible in a systematic basis set with moderate computational resources. Further computational savings can be achieved by exploiting the similarity of the adaptively contracted basis functions for closely related environments, e.g., in geometry optimizations or combined calculations of neutral and charged systems.
Structural stability and functional remodeling of high-density lipoproteins.
Gursky, Olga
2015-09-14
Lipoproteins are protein-lipid nanoparticles that transport lipids in circulation and are central in atherosclerosis and other disorders of lipid metabolism. Apolipoproteins form flexible structural scaffolds and important functional ligands on the particle surface and direct lipoprotein metabolism. Lipoproteins undergo multiple rounds of metabolic remodeling that is crucial to lipid transport. Important aspects of this remodeling, including apolipoprotein dissociation and particle fusion, are mimicked in thermal or chemical denaturation and are modulated by free energy barriers. Here we review the biophysical studies that revealed the kinetic mechanism of lipoprotein stabilization and unraveled its structural basis. The main focus is on high-density lipoprotein (HDL). An inverse correlation between stability and functions of various HDLs in cholesterol transport suggests the functional role of structural disorder. A mechanism for the conformational adaptation of the major HDL proteins, apoA-I and apoA-II, to the increasing lipid load is proposed. Together, these studies help understand why HDL forms discrete subclasses separated by kinetic barriers, which have distinct composition, conformation and functional properties. Understanding these properties may help improve HDL quality and develop novel therapies for cardiovascular disease. PMID:25749369
NASA Astrophysics Data System (ADS)
Mattsson, Thomas R.
2007-06-01
Atomistic simulations employing Density Functional Theory (DFT) have recently emerged as a powerful way of increasing our understanding of materials and processes in high energy density physics. Knowledge of the properties of water (equation of state, electrical conductivity, diffusion, low-energy opacity) is essential for correctly describing the physics of giant planets as well as shock waves in water. Although a qualitative picture of water electrical conductivity has emerged, the necessary quantitative information is scarce over a wide range of temperature and density. Since experiments can only access certain areas of phase space, and often require modeling as a part of the analysis, Quantum Molecular Dynamics simulations play a vital role. Using finite-temperature density functional theory (FT-DFT), we have investigated the structure and electronic conductivity of water across three phase transitions (molecular liquid/ ionic liquid/ superionic/ electronic liquid). The ionic contribution to the conduction is calculated from proton diffusion and the electronic contribution is calculated using the Kubo-Greenwood formula. The calculations are performed with VASP, a plane-wave pseudo-potential code. There is a rapid transition to ionic conduction at 2000 K and 2 g/cm^3, whereas electronic conduction dominates at temperatures at and above 6000 K&[tilde;1]. Contrary to earlier results using the Car-Parrinello method&[tilde;2], we predict that the fluid bordering the superionic phase is conducting above 4000 K and 100 GPa. Our comprehensive use of FT-DFT explains the new findings. The calculated conductivity is compared to experimental data. I gratefully acknowledge Mike Desjarlais, my collaborator in this effort. The LDRD office at Sandia supported this work. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL
NASA Astrophysics Data System (ADS)
Ulian, Gianfranco; Valdrè, Giovanni
2015-07-01
Pyrophyllite has a significant role in both geophysics as a hydrous phase, which can recycle water into the Earth's mantle, and many industrial applications, such as petroleum and civil engineering. However, very few works have been proposed to fully characterize the thermodynamic properties of this mineral, especially at atomic scale. In the present work, we report structural, vibrational, thermochemical and thermophysical properties of pyrophyllite, calculated at the density functional theory level with the hybrid B3LYP functional, all-electron Gaussian-type orbitals and taking into account a correction to include dispersive forces. V( P, T) data at 300 K fit with isothermal third-order Birch-Murnaghan equations of state and yield K T 0 = 46.57 GPa, K' = 10.51 and V 0 = 213.67 Å3, where K T 0 is the thermal bulk modulus at 0 GPa, K' is the first derivative and V 0 is the volume at zero pressure, in very good agreement with recent experimental results obtained by in situ single-crystal synchrotron XRD. The compressional behaviour is highly anisotropic, with axial compressibility in ratio β( a):β( b):β( c) = 1.218:1.000:4.188. Pyrophyllite bulk modulus, thermal expansion coefficients and heat capacity at different P- T conditions are provided. The results of this kind of analysis can be useful in both geophysical and technological applications of the mineral and expand the high-temperature and high-pressure knowledge of this phase at physical conditions that are still difficult to obtain by experimental means. The simulated vibrational spectrum can also be used as a guideline by other authors in their experimental investigation of pyrophyllite.
Vidya, R.; Ravindran, P.; Fjellvaag, H.; Svensson, B. G.; Monakhov, E.; Ganchenkova, M.; Nieminen, R. M.
2011-01-15
Formation energies of various intrinsic defects and defect complexes in ZnO have been calculated using a density-functional-theory-based pseudopotential all-electron method. The various defects considered are oxygen vacancy (V{sub O}), zinc vacancy (V{sub Zn}), oxygen at an interstitial site (O{sub i}), Zn at an interstitial site (Zn{sub i}), Zn at V{sub O} (Zn{sub O}), O at V{sub Zn}(O{sub Zn}), and an antisite pair (combination of the preceding two defects). In addition, defect complexes like (V{sub O}+Zn{sub i}) and Zn-vacancy clusters are studied. The Schokkty pair (V{sub O}+V{sub Zn}) and Frenkel pairs [(V{sub O}+O{sub i}) and (V{sub Zn}+Zn{sub i})] are considered theoretically for the first time. Upon comparing the formation energies of these defects, we find that V{sub O} would be the dominant intrinsic defect under both Zn-rich and O-rich conditions and it is a deep double donor. Both Zn{sub O} and Zn{sub i} are found to be shallow donors. The low formation energy of donor-type intrinsic defects could lead to difficulty in achieving p-type conductivity in ZnO. Defect complexes have charge transitions deep inside the band gap. The red, yellow, and green photoluminescence peaks of undoped samples can be assigned to some of the defect complexes considered. It is believed that the red luminescence originates from an electronic transition in V{sub O}, but we find that it can originate from the antisite Zn{sub O} defect. Charge density and electron-localization function analyses have been used to understand the effect of these defects on the ZnO lattice. The electronic structure of ZnO with intrinsic defects has been studied using density-of-states and electronic band structure plots. The acceptor levels introduced by V{sub Zn} are relatively localized, making it difficult to achieve p-type conductivity with sufficient hole mobility.
Introducing PROFESS: A new program for orbital-free density functional theory calculations
NASA Astrophysics Data System (ADS)
Ho, Gregory S.; Lignères, Vincent L.; Carter, Emily A.
2008-12-01
We present PROFESS (PRinceton Orbital-Free Electronic Structure Software), a new software package that performs orbital-free density functional theory (OF-DFT) calculations. OF-DFT is a first principles quantum mechanics method primarily for condensed matter that can be made to scale linearly with system size. We describe the implementation of energy, force, and stress functionals and the methods used to optimize the electron density under periodic boundary conditions. All electronic energy and potential terms scale linearly while terms involving the ions exhibit quadratic scaling in our code. Despite the latter scaling, the program can treat tens of thousands of atoms with quantum mechanics on a single processor, as we demonstrate here. Limitations of the method are also outlined, the most serious of which is the accuracy of state-of-the-art kinetic energy functionals, which limits the applicability of the method to main group elements at present. Program summaryProgram title: PROFESS Catalogue identifier: AEBN_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEBN_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 35 933 No. of bytes in distributed program, including test data, etc.: 329 924 Distribution format: tar.gz Programming language: Fortran 90 Computer: Intel with ifort; AMD Opteron with pathf90 Operating system: Linux RAM: Problem dependent, but 2 GB is sufficient for up to 10,000 ions Classification: 7.3 External routines: FFTW ( http://www.fftw.org), MINPACK-2 Nature of problem: Given a set of coordinates describing the initial ion positions under periodic boundary conditions, recovers the ground state energy, electron density, ion positions, and cell lattice vectors predicted by orbital-free density functional theory. Except for computation of the
Density functional theory based generalized effective fragment potential method
Nguyen, Kiet A. E-mail: ruth.pachter@wpafb.af.mil; Pachter, Ruth E-mail: ruth.pachter@wpafb.af.mil; Day, Paul N.
2014-06-28
We present a generalized Kohn-Sham (KS) density functional theory (DFT) based effective fragment potential (EFP2-DFT) method for the treatment of solvent effects. Similar to the original Hartree-Fock (HF) based potential with fitted parameters for water (EFP1) and the generalized HF based potential (EFP2-HF), EFP2-DFT includes electrostatic, exchange-repulsion, polarization, and dispersion potentials, which are generated for a chosen DFT functional for a given isolated molecule. The method does not have fitted parameters, except for implicit parameters within a chosen functional and the dispersion correction to the potential. The electrostatic potential is modeled with a multipolar expansion at each atomic center and bond midpoint using Stone's distributed multipolar analysis. The exchange-repulsion potential between two fragments is composed of the overlap and kinetic energy integrals and the nondiagonal KS matrices in the localized molecular orbital basis. The polarization potential is derived from the static molecular polarizability. The dispersion potential includes the intermolecular D3 dispersion correction of Grimme et al. [J. Chem. Phys. 132, 154104 (2010)]. The potential generated from the CAMB3LYP functional has mean unsigned errors (MUEs) with respect to results from coupled cluster singles, doubles, and perturbative triples with a complete basis set limit (CCSD(T)/CBS) extrapolation, of 1.7, 2.2, 2.0, and 0.5 kcal/mol, for the S22, water-benzene clusters, water clusters, and n-alkane dimers benchmark sets, respectively. The corresponding EFP2-HF errors for the respective benchmarks are 2.41, 3.1, 1.8, and 2.5 kcal/mol. Thus, the new EFP2-DFT-D3 method with the CAMB3LYP functional provides comparable or improved results at lower computational cost and, therefore, extends the range of applicability of EFP2 to larger system sizes.
Density functional theory based generalized effective fragment potential method.
Nguyen, Kiet A; Pachter, Ruth; Day, Paul N
2014-06-28
We present a generalized Kohn-Sham (KS) density functional theory (DFT) based effective fragment potential (EFP2-DFT) method for the treatment of solvent effects. Similar to the original Hartree-Fock (HF) based potential with fitted parameters for water (EFP1) and the generalized HF based potential (EFP2-HF), EFP2-DFT includes electrostatic, exchange-repulsion, polarization, and dispersion potentials, which are generated for a chosen DFT functional for a given isolated molecule. The method does not have fitted parameters, except for implicit parameters within a chosen functional and the dispersion correction to the potential. The electrostatic potential is modeled with a multipolar expansion at each atomic center and bond midpoint using Stone's distributed multipolar analysis. The exchange-repulsion potential between two fragments is composed of the overlap and kinetic energy integrals and the nondiagonal KS matrices in the localized molecular orbital basis. The polarization potential is derived from the static molecular polarizability. The dispersion potential includes the intermolecular D3 dispersion correction of Grimme et al. [J. Chem. Phys. 132, 154104 (2010)]. The potential generated from the CAMB3LYP functional has mean unsigned errors (MUEs) with respect to results from coupled cluster singles, doubles, and perturbative triples with a complete basis set limit (CCSD(T)/CBS) extrapolation, of 1.7, 2.2, 2.0, and 0.5 kcal/mol, for the S22, water-benzene clusters, water clusters, and n-alkane dimers benchmark sets, respectively. The corresponding EFP2-HF errors for the respective benchmarks are 2.41, 3.1, 1.8, and 2.5 kcal/mol. Thus, the new EFP2-DFT-D3 method with the CAMB3LYP functional provides comparable or improved results at lower computational cost and, therefore, extends the range of applicability of EFP2 to larger system sizes. PMID:24985612
Density functional calculation for Li2CuSn as an electrode material for rechargeable batteries.
Reshak, Ali Hussain; Ordóñez Ortíz, Diego Andrés
2009-10-01
The all electron full potential linearized augmented plane wave method has been used for an ab initio theoretical study of the band structure, density of states and electron charge density, and the spectral features of the linear and nonlinear optical susceptibilities for the host CuSn and Li(2)CuSn compounds. We have calculated the density of states at Fermi energy and the electronic specific heat coefficient (gamma). The total charge densities in the (100) and (110) planes were calculated. We noticed that inserting Li into CuSn leads to give two structures in the spectral features of the linear optical susceptibilities while the host compound gives only one structure. Insertion of Li into CuSn leads to breaking the symmetry resulting in noncentrosymmetric material. We have calculated the complex second-order nonlinear optical susceptibility tensor for the intercalated compound. PMID:19754092
NASA Astrophysics Data System (ADS)
Schoonmaker, Robert; Clark, Stewart; Lancaster, Tom; Frawley, Thomas; Hatton, Peter
Iron arsenide intersects interesting physics between novel superconductors and other helical magnetic ordering in Pnma metal arsenide materials. Recent diffraction data has found a more complex ordering than a simple helical incommensurate spin density wave. Instead iron arsenide exhibits a definite chirality to the helimagnetism, an ellipticity in the spiral not aligned with the crystal axis, and resonant diffraction peaks forbidden by the Pnma symmetry. From non-magnetic and collinear density functional theory calculations we present insight into the mechanisms for the formation of this helimagnetic state. We find that ferromagnetic superexchange is a likely mechanism for the spin ordering and that the noncollinear ordering under this regime is caused by the spins on neighbouring irons arranging to minimise direct exchange between iron atoms, and also minimize disruption of the ferromagnetic superexchange between priveleged iron-arsenic pairs. To explain the forbidden peaks in the diffraction we have performed second-order spin-orbit perturbation calculations on the nonmagnetic calculation, which finds that the orbital ordering on the iron atoms coupled to the helimagnetism will lead to the otherwise symmetry-forbidden peaks.
Specification of optical components using the power spectral density function
Lawson, J.K.; Wolfe, C.R.; Manes, K.R.; Trenholme, J.B.; Aikens, D.M.; English, R.E. Jr.
1995-06-20
This paper describes the use of Fourier techniques to characterize the wavefront of optical components, specifically, the use of the power spectral density, (PSD), function. The PSDs of several precision optical components will be shown. Many of the optical components of interest to us have square, rectangular or irregularly shaped apertures with major dimensions up-to 800 mm. The wavefronts of components with non-circular apertures cannot be analyzed with Zernicke polynomials since these functions are an orthogonal set for circular apertures only. Furthermore, Zernicke analysis is limited to treating low frequency wavefront aberrations; mid-spatial scale and high frequency error are expressed only as ``residuals.`` A more complete and powerful representation of the optical wavefront can be obtained by Fourier analysis in 1 or 2 dimensions. The PSD is obtained from the amplitude of frequency components present in the Fourier spectrum. The PSD corresponds to the scattered intensity as a function of scattering angle in the wavefront and can be used to describe the intensity distribution at focus. The shape of a resultant wavefront or the focal spot of a complex multi-component laser system can be calculated and optimized using the PSDs of individual optical components which comprise it.
Effective quadrupole-quadrupole interaction from density functional theory
NASA Astrophysics Data System (ADS)
Alhassid, Y.; Bertsch, G. F.; Fang, L.; Sabbey, B.
2006-09-01
The density functional theory of nuclear structure provides a many-particle wave function that is useful for static properties, but an extension of the theory is necessary to describe correlation effects or other dynamic properties. We propose a procedure to extend the theory by mapping the properties of a self-consistent mean-field theory onto an effective shell-model Hamiltonian with quadrupole-quadrupole interaction. In this initial study, we consider the sd-shell nuclei Ne20, Mg24, Si28, and Ar36. The method is first tested with the USD shell-model Hamiltonian, using its mean-field approximation to construct an effective Hamiltonian and partially recover correlation effects. We find that more than half of the correlation energy is due to the quadrupole interaction. We then follow a similar procedure but using the SLy4 Skyrme energy functional as our starting point and truncating the space to the spherical sd shell. The constructed shell-model Hamiltonian is found to satisfy minimal consistency requirements to reproduce the properties of the mean-field solution. The quadrupolar correlation energies computed with the mapped Hamiltonian are reasonable compared with those computed by other methods. The method also provides a well-defined renormalization of the quadrupole operator in the shell-model space, the “effective charge” of the phenomenological shell model.
Density-functional theory: time to move up?
NASA Astrophysics Data System (ADS)
Marzari, Nicola
2013-03-01
Materials' simulations based on density-functional theory (DFT) have become an extremely powerful and widely used tool for scientific discovery and technological advancement. Still, in the current approximations, they remain an imperfect tool for predicting materials' properties, with open and urgent challenges in the quest towards qualitative and quantitative accuracy. Several of these challenges stem from the remnants of self-interaction in the electronic-structure framework, leading to qualitative failures in describing some of the fundamental processes involved e.g. in energy applications - from charge-transfer excitations to photoemission spectra to the structure and reactivity of transition-metal complexes. I'll discuss these challenges in realistic case studies, and present a brief overview of some of our suggestions for possible solutions - including constrained DFT, DFT + onsite and intersite Hubbard terms, and Koopmans' compliant energy functionals. In particular, I'll highlight how Koopmans' compliant functionals point to a beyond-DFT formulation where both total energies and spectroscopic properties can be accounted for. Such framework will be illustrated with applications to real systems and with simplified models that can be solved exactly. Work done in collaboration with Patrick H-L Sit, Heather Kulik, Damian Scherlis, Matteo Cococcioni, Ismaila Dabo, Andrea Ferretti, Nicolas Poilvert, Cheol-Hwan Park, Giovanni Borghi, and Linh Nguyen.
Probability Density Functions of Observed Rainfall in Montana
NASA Technical Reports Server (NTRS)
Larsen, Scott D.; Johnson, L. Ronald; Smith, Paul L.
1995-01-01
The question of whether a rain rate probability density function (PDF) can vary uniformly between precipitation events is examined. Image analysis on large samples of radar echoes is possible because of advances in technology. The data provided by such an analysis easily allow development of radar reflectivity factors (and by extension rain rate) distribution. Finding a PDF becomes a matter of finding a function that describes the curve approximating the resulting distributions. Ideally, one PDF would exist for all cases; or many PDF's that have the same functional form with only systematic variations in parameters (such as size or shape) exist. Satisfying either of theses cases will, validate the theoretical basis of the Area Time Integral (ATI). Using the method of moments and Elderton's curve selection criteria, the Pearson Type 1 equation was identified as a potential fit for 89 percent of the observed distributions. Further analysis indicates that the Type 1 curve does approximate the shape of the distributions but quantitatively does not produce a great fit. Using the method of moments and Elderton's curve selection criteria, the Pearson Type 1 equation was identified as a potential fit for 89% of the observed distributions. Further analysis indicates that the Type 1 curve does approximate the shape of the distributions but quantitatively does not produce a great fit.
Building A Universal Nuclear Energy Density Functional (UNEDF)
Joe Carlson; Dick Furnstahl; Mihai Horoi; Rusty Lusk; Witek Nazarewicz; Esmond Ng; Ian Thompson; James Vary
2012-09-30
During the period of Dec. 1 2006 - Jun. 30, 2012, the UNEDF collaboration carried out a comprehensive study of all nuclei, based on the most accurate knowledge of the strong nuclear interaction, the most reliable theoretical approaches, the most advanced algorithms, and extensive computational resources, with a view towards scaling to the petaflop platforms and beyond. The long-term vision initiated with UNEDF is to arrive at a comprehensive, quantitative, and unified description of nuclei and their reactions, grounded in the fundamental interactions between the constituent nucleons. We seek to replace current phenomenological models of nuclear structure and reactions with a well-founded microscopic theory that delivers maximum predictive power with well-quantified uncertainties. Specifically, the mission of this project has been three-fold: first, to find an optimal energy density functional (EDF) using all our knowledge of the nucleonic Hamiltonian and basic nuclear properties; second, to apply the EDF theory and its extensions to validate the functional using all the available relevant nuclear structure and reaction data; third, to apply the validated theory to properties of interest that cannot be measured, in particular the properties needed for reaction theory. The main physics areas of UNEDF, defined at the beginning of the project, were: ab initio structure; ab initio functionals; DFT applications; DFT extensions; reactions.
Schwalbe, Sebastian; Trepte, Kai; Seifert, Gotthard; Kortus, Jens
2016-03-01
We present a first principles study of low-spin (LS)/high-spin (HS) screening for 3d metal centers in the metal organic framework (MOF) DUT-8(Ni). Various density functional theory (DFT) codes have been used to evaluate numerical and DFT related errors. We compare highly accurate all-electron implementations with the widely used plane wave approach. We present electronically and magnetically stable DUT-8(Ni) HS secondary building units (SBUs). In this work we show how to tune the magnetic and electronic properties of the original SBU only by changing the metal centers. PMID:26922864
A Density Functional Theory Study of Formaldehyde Adsorption on Ceria
Mei, Donghai; Deskins, N. Aaron; Dupuis, Michel
2007-11-01
Molecular adsorption of formaldehyde on the stoichiometric CeO2(111) and CeO2(110) surfaces was studied using periodic density functional theory. Two adsorption modes (strong chemisorbed and weak physisorbed) were identified on both surfaces. This is consistent with recent experimental observations. On the (111) surface, formaldehyde strongly chemisorbs with an adsorption energy of 0.86 eV to form a dioxymethylene-like structure, in which a surface O lifts from the surface to bind with the C of formaldehyde. A weak physisorbed state with adsorption energy of 0.28 eV was found with the O of formaldehyde interacting with a surface Ce. On the (110) surface, dioxymethyelene formation was also observed, with an adsorption energy of 1.31 eV. The weakly adsorbed state of formaldehyde on the (110) surface was energetically comparable to the weak adsorption state on the (111) surface, but adsorption occurred through a formaldehyde C and surface O interaction. Analysis of the local density of states and charge density differences after adsorption shows that strong covalent bonding occurs between the C of formaldehyde and surface O when dioxymethylene forms. Calculated vibrational frequencies also confirm dioxymethylene formation. Our results also show that as the coverage increases, the adsorption of formaldehyde on the (111) surface becomes weak, but is nearly unaffected on the (110) surface. This work was supported by a Laboratory Directed Research and Development (LDRD) project of the Pacific Northwest National Laboratory (PNNL). The computations were performed using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory, which is a U.S. Department of Energy national scientific user facility located at PNNL in Richland, Washington. Computing time was made under a Computational Grand Challenge “Computational Catalysis”. Part of the computing time was also granted by the National Energy Research Scientific Computing
Hierarchy of equations for the energy functional of the density-functional theory
NASA Astrophysics Data System (ADS)
Nagy, Á.
1993-04-01
A hierarchy of equations has been derived for the energy functionals of the density-functional theory using the virial theorem and the Levy-Perdew relation. In the local-density approximation, the solution of the equations of hierarchy for the kinetic and exchange energies provides the well-known Thomas-Fermi expression for the kinetic energy and the Slater-Gáspár-Kohn-Sham expression for the exchange. The truncation of the hierarchies of the kinetic and exchange energies results in rigorous lower bounds to the kinetic energy and upper bounds to the exchange energy in the plane-wave approximation.
Ionospheric mapping functions based on electron density fields
NASA Astrophysics Data System (ADS)
Zus, Florian; Deng, Zhiguo; Heise, Stefan; Wickert, Jens
2016-04-01
We developed an ionospheric Mapping Function (MF) for the Global Navigation Satellite System (GNSS) which is based on the electron density field of the International Reference Ionosphere (IRI). The station specific MF utilizes a look-up table which contains a set of ray-traced ionospheric delays. Hence, unlike the simple MFs that are currently in use, the developed MF depends on the time, location, elevation and azimuth angle. Ray-bending is taken into account, which implies that the MF depends on the carrier frequency as well. This frequency dependency of the MF can be readily used to examine higher-order ionospheric effects due to ray-bending. We compare the proposed MF with the so-called single layer model MF and find significant differences in particular around the equatorial anomaly. In so-far as the proposed MF is based on a realistic electron density field (IRI) our comparison shows the potential error of the single-layer model MF in practice. We conclude that the developed MF concept might be valuable in the GNSS Total Electron Content estimation. The frequency dependency of the MF can be used to mitigate higher-order ionospheric effects.
Density functional theory and phytochemical study of 8-hydroxyisodiospyrin
NASA Astrophysics Data System (ADS)
Ullah, Zakir; Ata-ur-Rahman; Fazl-i-Sattar; Rauf, Abdur; Yaseen, Muhammad; Hassan, Waseem; Tariq, Muhammad; Ayub, Khurshid; Tahir, Asif Ali; Ullah, Habib
2015-09-01
Comprehensive theoretical and experimental studies of a natural product, 8-hydroxyisodiospyrin (HDO) have been carried out. Based on the correlation of experimental and theoretical data, an appropriate computational model was developed for obtaining the electronic, spectroscopic, and thermodynamic parameters of HDO. First of all, the exact structure of HDO is confirmed from the nice correlation of theory and experiment, prior to determination of its electroactive nature. Hybrid density functional theory (DFT) is employed for all theoretical simulations. The experimental and predicted IR and UV-vis spectra [B3LYP/6-31+G(d,p) level of theory] have excellent correlation. Inter-molecular non-covalent interaction of HDO with different gases such as NH3, CO2, CO, H2O is investigated through geometrical counterpoise (gCP) i.e., B3LYP-gCP-D3/6-31G∗ method. Furthermore, the inter-molecular interaction is also supported by geometrical parameters, electronic properties, thermodynamic parameters and charge analysis. All these characterizations have corroborated each other and confirmed the electroactive nature (non-covalent interaction ability) of HDO for the studied gases. Electronic properties such as Ionization Potential (IP), Electron Affinities (EA), electrostatic potential (ESP), density of states (DOS), HOMO, LUMO, and band gap of HDO have been estimated for the first time theoretically.
Accurate ionization potential of semiconductors from efficient density functional calculations
NASA Astrophysics Data System (ADS)
Ye, Lin-Hui
2016-07-01
Despite its huge successes in total-energy-related applications, the Kohn-Sham scheme of density functional theory cannot get reliable single-particle excitation energies for solids. In particular, it has not been able to calculate the ionization potential (IP), one of the most important material parameters, for semiconductors. We illustrate that an approximate exact-exchange optimized effective potential (EXX-OEP), the Becke-Johnson exchange, can be used to largely solve this long-standing problem. For a group of 17 semiconductors, we have obtained the IPs to an accuracy similar to that of the much more sophisticated G W approximation (GWA), with the computational cost of only local-density approximation/generalized gradient approximation. The EXX-OEP, therefore, is likely as useful for solids as for finite systems. For solid surfaces, the asymptotic behavior of the vx c has effects similar to those of finite systems which, when neglected, typically cause the semiconductor IPs to be underestimated. This may partially explain why standard GWA systematically underestimates the IPs and why using the same GWA procedures has not been able to get an accurate IP and band gap at the same time.
Density functional theory for protein transfer free energy.
Mills, Eric A; Plotkin, Steven S
2013-10-24
We cast the problem of protein transfer free energy within the formalism of density functional theory (DFT), treating the protein as a source of external potential that acts upon the solvent. Solvent excluded volume, solvent-accessible surface area, and temperature dependence of the transfer free energy all emerge naturally within this formalism, and may be compared with simplified "back of the envelope" models, which are also developed here. Depletion contributions to osmolyte induced stability range from 5 to 10 kBT for typical protein lengths. The general DFT transfer theory developed here may be simplified to reproduce a Langmuir isotherm condensation mechanism on the protein surface in the limits of short-ranged interactions, and dilute solute. Extending the equation of state to higher solute densities results in non-monotonic behavior of the free energy driving protein or polymer collapse. Effective interaction potentials between protein backbone or side chains and TMAO are obtained, assuming a simple backbone/side chain two-bead model for the protein with an effective 6-12 potential with the osmolyte. The transfer free energy δg shows significant entropy: d(δg)/dT ≈ 20 kB for a 100-residue protein. The application of DFT to effective solvent forces for use in implicit-solvent molecular dynamics is also developed. The simplest DFT expressions for implicit-solvent forces contain both depletion interactions and an "impeded-solvation" repulsive force at larger distances. PMID:23944753
Kinetic Density Functional Theory: A Microscopic Approach to Fluid Mechanics
NASA Astrophysics Data System (ADS)
Umberto Marini Bettolo, Marconi; Simone, Melchionna
2014-10-01
In the present paper we give a brief summary of some recent theoretical advances in the treatment of inhomogeneous fluids and methods which have applications in the study of dynamical properties of liquids in situations of extreme confinement, such as nanopores, nanodevices, etc. The approach obtained by combining kinetic and density functional methods is microscopic, fully self-consistent and allows to determine both configurational and flow properties of dense fluids. The theory predicts the correct hydrodynamic behavior and provides a practical and numerical tool to determine how the transport properties are modified when the length scales of the confining channels are comparable with the size of the molecules. The applications range from the dynamics of simple fluids under confinement, to that of neutral binary mixtures and electrolytes where the theory in the limit of slow gradients reproduces the known phenomenological equations such as the Planck—Nernst—Poisson and the Smolochowski equations. The approach here illustrated allows for fast numerical solution of the evolution equations for the one-particle phase-space distributions by means of the weighted density lattice Boltzmann method and is particularly useful when one considers flows in complex geometries.
Pairing Nambu-Goldstone Modes within Nuclear Density Functional Theory.
Hinohara, Nobuo; Nazarewicz, Witold
2016-04-15
We show that the Nambu-Goldstone formalism of the broken gauge symmetry in the presence of the T=1 pairing condensate offers a quantitative description of the binding-energy differences of open-shell superfluid nuclei. We conclude that the pairing-rotational moments of inertia are excellent pairing indicators, which are free from ambiguities attributed to odd-mass systems. We offer a new, unified interpretation of the binding-energy differences traditionally viewed in the shell model picture as signatures of the valence nucleon properties. We present the first systematic analysis of the off-diagonal pairing-rotational moments of inertia and demonstrate the mixing of the neutron and proton pairing-rotational modes in the ground states of even-even nuclei. Finally, we discuss the importance of mass measurements of neutron-rich nuclei for constraining the pairing energy density functional. PMID:27127964
Nitrotyrosine adsorption on defective graphene: A density functional theory study
NASA Astrophysics Data System (ADS)
Majidi, R.; Karami, A. R.
2015-06-01
We have applied density functional theory to study adsorption of nitrotyrosine on perfect and defective graphene sheets. The graphene sheets with Stone-Wales (SW) defect, pentagon-nonagon (5-9) single vacancy, and pentagon-octagon-pentagon (5-8-5) double vacancy were considered. The calculations of adsorption energy showed that nitrotyrosine presents a more strong interaction with defective graphene rather than with perfect graphene sheet. The order of interaction strength is: SW>5-9>5-8-5>perfect graphene. It is found that the electronic properties of perfect and defective graphene are sensitive to the presence of nitrotyrosine. Hence, graphene sheets can be considered as a good sensor for detection of nitrotyrosine molecule which is observed in connection with several human disorders, such as Parkinson's and Alzheimer's disease.
Band Anticrossing in Dilute Germanium Carbides Using Hybrid Density Functionals
NASA Astrophysics Data System (ADS)
Stephenson, Chad A.; O'brien, William A.; Qi, Meng; Penninger, Michael; Schneider, William F.; Wistey, Mark A.
2016-04-01
Dilute germanium carbides (Ge1- x C x ) offer a direct bandgap for compact silicon photonics, but widely varying properties have been reported. This work reports improved band structure calculations for Ge1- x C x using ab initio simulations that employ the HSE06 exchange-correlation density functional. Contrary to Vegard's law, the conduction band minimum at Γ is consistently found to decrease with increasing C content, while L and X valleys change much more slowly. The calculated Ge bandgap is within 11% of experimental values. A decrease in energy at the Γ conduction band valley of (170 meV ± 50)/%C is predicted, leading to a direct bandgap for x > 0.008. These results indicate a promising material for Group IV lasers.
Native defects in Tl6SI4: Density functional calculations
Shi, Hongliang; Du, Mao -Hua
2015-05-05
In this study, Tl6SI4 is a promising room-temperature semiconductor radiation detection material. Here, we report density functional calculations of native defects and dielectric properties of Tl6SI4. Formation energies and defect levels of native point defects and defect complexes are calculated. Donor-acceptor defect complexes are shown to be abundant in Tl6SI4. High resistivity can be obtained by Fermi level pinning by native donor and acceptor defects. Deep donors that are detrimental to electron transport are identified and methods to mitigate such problem are discussed. Furthermore, we show that mixed ionic-covalent character of Tl6SI4 gives rise to enhanced Born effective charges andmore » large static dielectric constant, which provides effective screening of charged defects and impurities.« less
Self-consistent polarization density functional theory: Application to Argon
Maerzke, Katie A.; Murdachaew, Garold; Mundy, Christopher J.; Schenter, Gregory K.; Siepmann, J. I.
2009-03-12
We present a comprehensive set of results for argon, a case study in weak interactions, using the selfconsistent polarization density functional theory (SCP-DFT). With minimal parameterization, SCPDFT is found is give excellent results for the dimer interaction energy, the second virial coefficient, the liquid structure, and the lattice constant and cohesion energy of the face-centered cubic (fcc) crystal compared to both accurate theoretical and experimental benchmarks. Thus, SCP-DFT holds promise as a fast, efficient, and accurate method for performing ab initio dynamics that include additional polarization and dispersion interactions for large, complex systems involving solvation and bond breaking. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.
β -decay study within multireference density functional theory and beyond
NASA Astrophysics Data System (ADS)
Konieczka, M.; Bączyk, P.; Satuła, W.
2016-04-01
A pioneering study of Gamow-Teller (GT) and Fermi matrix elements (MEs) using no-core-configuration-interaction formalism rooted in multireference density functional theory is presented. After a successful test performed for 6He→6Liβ decay, the model is applied to compute MEs in the s d - and p f -shell T =1 /2 mirror nuclei. The calculated GT MEs and the isospin-symmetry-breaking corrections to the Fermi branch are found to be in very good agreement with shell-model predictions in spite of fundamental differences between these models concerning model space, treatment of correlations, or inclusion of a core. This result indirectly supports the two-body-current-based scenarios behind the quenching of the axial-vector coupling constant.
Native defects in Tl6SI4: Density functional calculations
NASA Astrophysics Data System (ADS)
Shi, Hongliang; Du, Mao-Hua
2015-05-01
Tl6SI4 is a promising room-temperature semiconductor radiation detection material. Here, we report density functional calculations of native defects and dielectric properties of Tl6SI4. Formation energies and defect levels of native point defects and defect complexes are calculated. Donor-acceptor defect complexes are shown to be abundant in Tl6SI4. High resistivity can be obtained by Fermi level pinning by native donor and acceptor defects. Deep donors that are detrimental to electron transport are identified and methods to mitigate such problem are discussed. Furthermore, we show that mixed ionic-covalent character of Tl6SI4 gives rise to enhanced Born effective charges and large static dielectric constant, which provides effective screening of charged defects and impurities.
Density functional calculations of Hubbard parameter in actinide series
Puri, A.; Sen, K.D.
1993-05-01
The calculations of Hubbard parameter, U, which defines the polar state formation energy of the reaction 2(5f{sup n} 6d{sup 1} 7d{sup 2}) {yields} 5f{sup n-1} 6d{sup 2}7s{sup 2} + 5f{sup n+1} 7s{sup 2} for the actinide atoms, Th-No, have been carried out using the self-interaction-corrected (SIC) quasi-relativistic local spin density (LSD) functional due to Perdew and Zunger. Based on the available bandwidth calculations for the 5f metals and its monotonically decreasing trend with increasing nuclear charge it is predicted that the 5f state is iterent in Th-Np beyond which it becomes localized. These calculations agree with the conclusions drawn earlier by Johansson using the semiempirical data.
Density Functional Exploration of C4H3N Isomers.
Custer, Thomas; Szczepaniak, Urszula; Gronowski, Marcin; Fabisiewicz, Emilia; Couturier-Tamburelli, Isabelle; Kołos, Robert
2016-07-28
Molecules having C4H3N stoichiometry are of astrophysical interest. Two of these, methylcyanoacetylene (CH3C3N) and its structural isomer allenyl cyanide (H2CCCHN), have been observed in interstellar space, while several more have been examined in laboratories. Here we describe, for a broad range of C4H3N isomers, density functional calculations (B3LYP/aug-cc-pVTZ) of molecular parameters including the energetics, geometries, rotational constants, electric dipole moments, polarizabilities, vibrational IR frequencies, IR absorption intensities, and Raman activities. Singlet-triplet splittings as well as singlet vertical electronic excitation energies are given for selected species. The identification of less stable C4H3N molecules, generated in ongoing spectroscopic experiments, relies heavily on these quantum chemical predictions. PMID:27341606
Reproducibility in density functional theory calculations of solids.
Lejaeghere, Kurt; Bihlmayer, Gustav; Björkman, Torbjörn; Blaha, Peter; Blügel, Stefan; Blum, Volker; Caliste, Damien; Castelli, Ivano E; Clark, Stewart J; Dal Corso, Andrea; de Gironcoli, Stefano; Deutsch, Thierry; Dewhurst, John Kay; Di Marco, Igor; Draxl, Claudia; Dułak, Marcin; Eriksson, Olle; Flores-Livas, José A; Garrity, Kevin F; Genovese, Luigi; Giannozzi, Paolo; Giantomassi, Matteo; Goedecker, Stefan; Gonze, Xavier; Grånäs, Oscar; Gross, E K U; Gulans, Andris; Gygi, François; Hamann, D R; Hasnip, Phil J; Holzwarth, N A W; Iuşan, Diana; Jochym, Dominik B; Jollet, François; Jones, Daniel; Kresse, Georg; Koepernik, Klaus; Küçükbenli, Emine; Kvashnin, Yaroslav O; Locht, Inka L M; Lubeck, Sven; Marsman, Martijn; Marzari, Nicola; Nitzsche, Ulrike; Nordström, Lars; Ozaki, Taisuke; Paulatto, Lorenzo; Pickard, Chris J; Poelmans, Ward; Probert, Matt I J; Refson, Keith; Richter, Manuel; Rignanese, Gian-Marco; Saha, Santanu; Scheffler, Matthias; Schlipf, Martin; Schwarz, Karlheinz; Sharma, Sangeeta; Tavazza, Francesca; Thunström, Patrik; Tkatchenko, Alexandre; Torrent, Marc; Vanderbilt, David; van Setten, Michiel J; Van Speybroeck, Veronique; Wills, John M; Yates, Jonathan R; Zhang, Guo-Xu; Cottenier, Stefaan
2016-03-25
The widespread popularity of density functional theory has given rise to an extensive range of dedicated codes for predicting molecular and crystalline properties. However, each code implements the formalism in a different way, raising questions about the reproducibility of such predictions. We report the results of a community-wide effort that compared 15 solid-state codes, using 40 different potentials or basis set types, to assess the quality of the Perdew-Burke-Ernzerhof equations of state for 71 elemental crystals. We conclude that predictions from recent codes and pseudopotentials agree very well, with pairwise differences that are comparable to those between different high-precision experiments. Older methods, however, have less precise agreement. Our benchmark provides a framework for users and developers to document the precision of new applications and methodological improvements. PMID:27013736
Fundamental gap of molecular crystals via constrained density functional theory
NASA Astrophysics Data System (ADS)
Droghetti, Andrea; Rungger, Ivan; Das Pemmaraju, Chaitanya; Sanvito, Stefano
2016-05-01
The energy gap of a molecular crystal is one of the most important properties since it determines the crystal charge transport when the material is utilized in electronic devices. This is, however, a quantity difficult to calculate and standard theoretical approaches based on density functional theory (DFT) have proven unable to provide accurate estimates. In fact, besides the well-known band-gap problem, DFT completely fails in capturing the fundamental gap reduction occurring when molecules are packed in a crystal structures. The failure has to be associated with the inability of describing the electronic polarization and the real space localization of the charged states. Here we describe a scheme based on constrained DFT, which can improve upon the shortcomings of standard DFT. The method is applied to the benzene crystal, where we show that accurate results can be achieved for both the band gap and also the energy level alignment.
Descriptions of carbon isotopes within the energy density functional theory
Ismail, Atef; Cheong, Lee Yen; Yahya, Noorhana; Tammam, M.
2014-10-24
Within the energy density functional (EDF) theory, the structure properties of Carbon isotopes are systematically studied. The shell model calculations are done for both even-A and odd-A nuclei, to study the structure of rich-neutron Carbon isotopes. The EDF theory indicates the single-neutron halo structures in {sup 15}C, {sup 17}C and {sup 19}C, and the two-neutron halo structures in {sup 16}C and {sup 22}C nuclei. It is also found that close to the neutron drip-line, there exist amazing increase in the neutron radii and decrease on the binding energies BE, which are tightly related with the blocking effect and correspondingly the blocking effect plays a significant role in the shell model configurations.
Time-Dependent Density Functional Theory for Universal Quantum Computation
NASA Astrophysics Data System (ADS)
Tempel, David
2015-03-01
In this talk, I will discuss how the theorems of TDDFT can be applied to a class of qubit Hamiltonians that are universal for quantum computation. The theorems of TDDFT applied to universal Hamiltonians imply that single-qubit expectation values can be used as the basic variables in quantum computation and information theory, rather than wavefunctions. From a practical standpoint this opens the possibility of approximating observables of interest in quantum computations directly in terms of single-qubit quantities (i.e. as density functionals). Additionally, I will discuss how TDDFT provides an exact prescription for simulating universal Hamiltonians with other universal Hamiltonians that have different, and possibly easier-to-realize two-qubit interactions.
Density functional theory studies of HCOOH decomposition on Pd(111)
NASA Astrophysics Data System (ADS)
Scaranto, Jessica; Mavrikakis, Manos
2016-08-01
The investigation of formic acid (HCOOH) decomposition on transition metal surfaces is important to derive useful insights for vapor phase catalysis involving HCOOH and for the development of direct HCOOH fuel cells (DFAFC). Here we present the results obtained from periodic, self-consistent, density functional theory (DFT-GGA) calculations for the elementary steps involved in the gas-phase decomposition of HCOOH on Pd(111). Accordingly, we analyzed the minimum energy paths for HCOOH dehydrogenation to CO2 + H2 and dehydration to CO + H2O through the carboxyl (COOH) and formate (HCOO) intermediates. Our results suggest that HCOO formation is easier than COOH formation, but HCOO decomposition is more difficult than COOH decomposition, in particular in the presence of co-adsorbed O and OH species. Therefore, both paths may contribute to HCOOH decomposition. CO formation goes mainly through COOH decomposition.
Kappa distribution and Probability Density Functions in Solar Wind
NASA Astrophysics Data System (ADS)
Jurac, S.
2004-12-01
A signature of a statistical intermittency is the presence of large deviations from the average value: this increased probability of finding extreme deviations is characterized by Probability Density Functions (PDFs) which exhibit non Gaussian power-law tails. Such power-law distributions were observed over decades in biology, chemistry, finance and other fields. Known examples include heartbeat histograms, price distribution, turbulent fluid flow and many other non-equilibrium systems. It is shown that the Kappa distribution represents a good description of PDFs observed in Solar wind. The asymmetric fluctuations in variance over time observed in solar wind PDFs are Gamma distributed. It is shown that, by assuming such a distribution of variance, the Kappa distribution can be analitically derived.
Pairing Nambu-Goldstone Modes within Nuclear Density Functional Theory
NASA Astrophysics Data System (ADS)
Hinohara, Nobuo; Nazarewicz, Witold
2016-04-01
We show that the Nambu-Goldstone formalism of the broken gauge symmetry in the presence of the T =1 pairing condensate offers a quantitative description of the binding-energy differences of open-shell superfluid nuclei. We conclude that the pairing-rotational moments of inertia are excellent pairing indicators, which are free from ambiguities attributed to odd-mass systems. We offer a new, unified interpretation of the binding-energy differences traditionally viewed in the shell model picture as signatures of the valence nucleon properties. We present the first systematic analysis of the off-diagonal pairing-rotational moments of inertia and demonstrate the mixing of the neutron and proton pairing-rotational modes in the ground states of even-even nuclei. Finally, we discuss the importance of mass measurements of neutron-rich nuclei for constraining the pairing energy density functional.
Origin of anomeric effect: A density functional steric analysis
Huang, Ying; Zhong, Ai-Guo; Yang, Qinsong; Liu, Shubin
2011-01-01
The anomeric effect (the tendency of heteroatomic substituents adjacent to a heteroatom within the cyclohexane ring to prefer the axial orientation instead of the sterically less hindered equatorial position) is traditionally explained through either the dipole moment repulsion or the hyperconjugation effect. In this work, by employing our recent work in density functional steric analysis, we provide a novel two-component explanation, which is consistent with the common belief in chemistry that the effect has a stereoelectronic origin. With α-D-glucopyranose as the prototype, we systematically explore its conformational space and generate 32 isomers, leading to a total of 80 axial–equatorial conformation pairs. The energy difference analysis of these pairs shows that while statistically speaking the tendency is valid, the anomeric effect is not always true and can be violated. Three energy components, exchange–correlation, classical electrostatic, and density functional steric, are found to be directly proportional to the total energy difference between axial and equatorial isomers. We also found that the total dipole moment change, not the hyperconjugation effect, is a reasonable indicator of the total energy difference. However, all these correlations alone are not strong enough to provide a compellingly convincing explanation for the general validity of the effect. With the help of strong correlations between energy components, an explanation with two energy components, steric and electrostatic, was proposed in this work. We show that the axial–equatorial energy difference in general, with the anomeric effect as a special case, is dictated by two factors of the stereoelectronic origin, steric hindrance and classical electrostaticinteractions, synchronously working together. Another explanation in terms of exchange–correlation and electrostaticinteractions has also been obtained in this work.
Experimental assessment of presumed filtered density function models
NASA Astrophysics Data System (ADS)
Stetsyuk, V.; Soulopoulos, N.; Hardalupas, Y.; Taylor, A. M. K. P.
2015-06-01
Measured filtered density functions (FDFs) as well as assumed beta distribution model of mixture fraction and "subgrid" scale (SGS) scalar variance z '' 2 ¯ , used typically in large eddy simulations, were studied by analysing experimental data, obtained from two-dimensional planar, laser induced fluorescence measurements in isothermal swirling turbulent flows at a constant Reynolds number of 29 000 for different swirl numbers (0.3, 0.58, and 1.07). Two-dimensional spatial filtering, by using a box filter, was performed in order to obtain the filtered variables, namely, resolved mean and "subgrid" scale scalar variance. These were used as inputs for assumed beta distribution of mixture fraction and top-hat FDF shape estimates. The presumed beta distribution model, top-hat FDF, and the measured filtered density functions were used to integrate a laminar flamelet solution in order to calculate the corresponding resolved temperature. The experimentally measured FDFs varied with the flow swirl number and both axial and radial positions in the flow. The FDFs were unimodal at flow regions with low SGS scalar variance, z '' 2 ¯ < 0.01, and bimodal at regions with high SGS variance, z '' 2 ¯ > 0.02. Bimodal FDF could be observed for a filter size of approximately 1.5-2 times the Batchelor scale. Unimodal FDF could be observed for a filter size as large as four times the Batchelor scale under well-mixed conditions. In addition, two common computational models (a gradient assumption and a scale similarity model) for the SGS scalar variance were used with the aim to evaluate their validity through comparison with the experimental data. It was found that the gradient assumption model performed generally better than the scale similarity one.
Current Density Functional Theory Using Meta-Generalized Gradient Exchange-Correlation Functionals.
Furness, James W; Verbeke, Joachim; Tellgren, Erik I; Stopkowicz, Stella; Ekström, Ulf; Helgaker, Trygve; Teale, Andrew M
2015-09-01
We present the self-consistent implementation of current-dependent (hybrid) meta-generalized gradient approximation (mGGA) density functionals using London atomic orbitals. A previously proposed generalized kinetic energy density is utilized to implement mGGAs in the framework of Kohn-Sham current density functional theory (KS-CDFT). A unique feature of the nonperturbative implementation of these functionals is the ability to seamlessly explore a wide range of magnetic fields up to 1 au (∼235 kT) in strength. CDFT functionals based on the TPSS and B98 forms are investigated, and their performance is assessed by comparison with accurate coupled-cluster singles, doubles, and perturbative triples (CCSD(T)) data. In the weak field regime, magnetic properties such as magnetizabilities and nuclear magnetic resonance shielding constants show modest but systematic improvements over generalized gradient approximations (GGA). However, in the strong field regime, the mGGA-based forms lead to a significantly improved description of the recently proposed perpendicular paramagnetic bonding mechanism, comparing well with CCSD(T) data. In contrast to functionals based on the vorticity, these forms are found to be numerically stable, and their accuracy at high field suggests that the extension of mGGAs to CDFT via the generalized kinetic energy density should provide a useful starting point for further development of CDFT approximations. PMID:26575912
NASA Astrophysics Data System (ADS)
Ono, Tomoya; Heide, Marcus; Atodiresei, Nicolae; Baumeister, Paul; Tsukamoto, Shigeru; Blügel, Stefan
2010-11-01
We have developed an efficient computational scheme utilizing the real-space finite-difference formalism and the projector augmented-wave (PAW) method to perform precise first-principles electronic-structure simulations based on the density-functional theory for systems containing transition metals with a modest computational effort. By combining the advantages of the time-saving double-grid technique and the Fourier-filtering procedure for the projectors of pseudopotentials, we can overcome the egg box effect in the computations even for first-row elements and transition metals, which is a problem of the real-space finite-difference formalism. In order to demonstrate the potential power in terms of precision and applicability of the present scheme, we have carried out simulations to examine several bulk properties and structural energy differences between different bulk phases of transition metals and have obtained excellent agreement with the results of other precise first-principles methods such as a plane-wave-based PAW method and an all-electron full-potential linearized augmented plane-wave (FLAPW) method.
Hoyer, Chad E; Gagliardi, Laura; Truhlar, Donald G
2015-11-01
Time-dependent Kohn-Sham density functional theory (TD-KS-DFT) is useful for calculating electronic excitation spectra of large systems, but the low-energy spectra are often complicated by artificially lowered higher-energy states. This affects even the lowest energy excited states. Here, by calculating the lowest energy spin-conserving excited state for atoms from H to K and for formaldehyde, we show that this problem does not occur in multiconfiguration pair-density functional theory (MC-PDFT). We use the tPBE on-top density functional, which is a translation of the PBE exchange-correlation functional. We compare to a robust multireference method, namely, complete active space second-order perturbation theory (CASPT2), and to TD-KS-DFT with two popular exchange-correlation functionals, PBE and PBE0. We find for atoms that the mean unsigned error (MUE) of MC-PDFT with the tPBE functional improves from 0.42 to 0.40 eV with a double set of diffuse functions, whereas the MUEs for PBE and PBE0 drastically increase from 0.74 to 2.49 eV and from 0.45 to 1.47 eV, respectively. PMID:26722961
A density functional for core-valence correlation energy
NASA Astrophysics Data System (ADS)
Ranasinghe, Duminda S.; Frisch, Michael J.; Petersson, George A.
2015-12-01
A density functional, ɛCV-DFT(ρc, ρv), describing the core-valence correlation energy has been constructed as a linear combination of ɛLY Pcorr(ρc), ɛV WN5corr(ρc, ρv), ɛPBEcorr(ρc, ρv), ɛSlaterex(ρc, ρv), ɛHCTHex(ρc, ρv), ɛHFex(ρc, ρv), and F CV -DFT (" separators=" N i , Z i ) , a function of the nuclear charges. This functional, with 6 adjustable parameters, reproduces (±0.27 kcal/mol rms error) a benchmark set of 194 chemical energy changes including 9 electron affinities, 18 ionization potentials, and 167 total atomization energies covering the first- and second-rows of the periodic table. This is almost twice the rms error (±0.16 kcal/mol) obtained with CCSD(T)/MTsmall calculations, but less than half the rms error (±0.65 kcal/mol) obtained with MP2/GTlargeXP calculations, and somewhat smaller than the rms error (±0.39 kcal/mol) obtained with CCSD/MTsmall calculations. The largest positive and negative errors from ɛCV-DFT(ρc, ρv) were 0.88 and -0.75 kcal/mol with the set of 194 core-valence energy changes ranging from +3.76 kcal/mol for the total atomization energy of propyne to -9.05 kcal/mol for the double ionization of Mg. Evaluation of the ɛCV-DFT(ρc, ρv) functional requires less time than a single SCF iteration, and the accuracy is adequate for any model chemistry based on the CCSD(T) level of theory.
Reduced density-matrix functional theory: Correlation and spectroscopy
Di Sabatino, S.; Romaniello, P.; Berger, J. A.; Reining, L.
2015-07-14
In this work, we explore the performance of approximations to electron correlation in reduced density-matrix functional theory (RDMFT) and of approximations to the observables calculated within this theory. Our analysis focuses on the calculation of total energies, occupation numbers, removal/addition energies, and spectral functions. We use the exactly solvable Hubbard dimer at 1/4 and 1/2 fillings as test systems. This allows us to analyze the underlying physics and to elucidate the origin of the observed trends. For comparison, we also report the results of the GW approximation, where the self-energy functional is approximated, but no further hypothesis is made concerning the approximations of the observables. In particular, we focus on the atomic limit, where the two sites of the dimer are pulled apart and electrons localize on either site with equal probability, unless a small perturbation is present: this is the regime of strong electron correlation. In this limit, using the Hubbard dimer at 1/2 filling with or without a spin-symmetry-broken ground state allows us to explore how degeneracies and spin-symmetry breaking are treated in RDMFT. We find that, within the used approximations, neither in RDMFT nor in GW, the signature of strong correlation is present, when looking at the removal/addition energies and spectral function from the spin-singlet ground state, whereas both give the exact result for the spin-symmetry broken case. Moreover, we show how the spectroscopic properties change from one spin structure to the other.
Electrochemical phase diagrams for Ti oxides from density functional calculations
NASA Astrophysics Data System (ADS)
Huang, Liang-Feng; Rondinelli, James M.
2015-12-01
Developing an accurate simulation method for the electrochemical stability of solids, as well as understanding the physics related with its accuracy, is critically important for improving the performance of compounds and predicting the stability of new materials in aqueous environments. Herein we propose a workflow for the accurate calculation of first-principles electrochemical phase (Pourbaix) diagrams. With this scheme, we study the electrochemical stabilities of Ti and Ti oxides using density-functional theory. First, we find the accuracy of an exchange-correlation functional in predicting formation energies and electrochemical stabilities is closely related with the electronic exchange interaction therein. Second, the metaGGA and hybrid functionals with a more precise description of the electronic exchange interaction lead to a systematic improvement in the accuracy of the Pourbaix diagrams. Furthermore, we show that accurate Ti Pourbaix diagrams also require that thermal effects are included through vibrational contributions to the free energy. We then use these diagrams to explain various experimental electrochemical phenomena for the Ti-O system, and show that if experimental formation energies for Ti oxides, which contain contributions from defects owing to their generation at high (combustion) temperatures, are directly used to predict room temperature Pourbaix diagrams then significant inaccuracies result. In contrast, the formation energies from accurate first-principles calculations, e.g., using metaGGA and hybrid functionals, are found to be more reliable. Finally, to facilitate the future application of our accurate electrochemical phase equilibria diagrams, the variation of the Ti Pourbaix diagrams with aqueous ion concentration is also provided.
A density functional for core-valence correlation energy.
Ranasinghe, Duminda S; Frisch, Michael J; Petersson, George A
2015-12-01
A density functional, εCV-DFT(ρc, ρv), describing the core-valence correlation energy has been constructed as a linear combination of εLY P (corr)(ρc), εV WN5 (corr)(ρc, ρv), εPBE (corr)(ρc, ρv), εSlater (ex)(ρc, ρv), εHCTH (ex)(ρc, ρv), εHF (ex)(ρc, ρv), and FCV-DFTNi,Zi, a function of the nuclear charges. This functional, with 6 adjustable parameters, reproduces (±0.27 kcal/mol rms error) a benchmark set of 194 chemical energy changes including 9 electron affinities, 18 ionization potentials, and 167 total atomization energies covering the first- and second-rows of the periodic table. This is almost twice the rms error (±0.16 kcal/mol) obtained with CCSD(T)/MTsmall calculations, but less than half the rms error (±0.65 kcal/mol) obtained with MP2/GTlargeXP calculations, and somewhat smaller than the rms error (±0.39 kcal/mol) obtained with CCSD/MTsmall calculations. The largest positive and negative errors from εCV-DFT(ρc, ρv) were 0.88 and -0.75 kcal/mol with the set of 194 core-valence energy changes ranging from +3.76 kcal/mol for the total atomization energy of propyne to -9.05 kcal/mol for the double ionization of Mg. Evaluation of the εCV-DFT(ρc, ρv) functional requires less time than a single SCF iteration, and the accuracy is adequate for any model chemistry based on the CCSD(T) level of theory. PMID:26646873
The QTP family of consistent functionals and potentials in Kohn-Sham density functional theory.
Jin, Yifan; Bartlett, Rodney J
2016-07-21
This manuscript presents the second, consistent density functional in the QTP (Quantum Theory Project) family, that is, the CAM-QTP(01). It is a new range-separated exchange-correlation functional in which the non-local exchange contribution is 100% at large separation. It follows the same basic principles of this family that the Kohn-Sham eigenvalues of the occupied orbitals approximately equal the vertical ionization energies, which is not fulfilled by most of the traditional density functional methods. This new CAM-QTP(01) functional significantly improves the accuracy of the vertical excitation energies especially for the Rydberg states in the test set. It also reproduces many other properties such as geometries, reaction barrier heights, and atomization energies. PMID:27448874
Designing Meaningful Density Functional Theory Calculations in Materials Science
NASA Astrophysics Data System (ADS)
Mattsson, A. E.
2005-07-01
Density functional theory (DFT) methods for calculating the quantum mechanical ground states of condensed matter systems are now a common and significant component of materials research. These methods are also increasingly used in Equation of State work, in particular in the warm dense matter regime. The growing importance of DFT reflects the development of sufficiently accurate functionals, efficient algorithms, and continuing improvements in computing capabilities. As the materials problems to which DFT is applied have become large and complex, so have the sets of calculations necessary to investigate a given problem. Highly versatile, powerful codes exist to serve the practitioner, but designing useful simulations is a complicated task, involving intricate manipulation of many variables, with many pitfalls for the unwary and the inexperienced. We give an overview of DFT and discuss several of the most important issues that go into designing a meaningful DFT calculation. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.
Metallophilic interactions from dispersion-corrected density-functional theory
Otero-de-la-Roza, Alberto Mallory, Joel D.; Johnson, Erin R.
2014-05-14
In this article, we present the first comprehensive study of metallophilic (aurophilic) interactions using dispersion-corrected density-functional theory. Dispersion interactions (an essential component of metallophilicity) are treated using the exchange-hole dipole moment (XDM) model. By comparing against coupled-cluster benchmark calculations on simple dimers, we show that LC-ωPBE-XDM is a viable functional to study interactions between closed-shell transition metals and that it performs uniformly better than second-order Møller-Plesset theory, the basic computational technique used in previous works. We apply LC-ωPBE-XDM to address several open questions regarding metallophilicity, such as the interplay between dispersion and relativistic effects, the interaction strength along group 11, the additivity of homo- and hetero-metallophilic effects, the stability of [E(AuPH{sub 3}){sub 4}]{sup +} cations (E = N, P, As, Sb), and the role of metallophilic effects in crystal packing. We find that relativistic effects explain the prevalence of aurophilicity not by stabilizing metal-metal contacts, but by preventing gold from forming ionic structures involving bridge anions (which are otherwise common for Ag and Cu) as a result of the increased electron affinity of the metal. Dispersion effects are less important than previously assumed and their stabilization contribution is relatively independent of the metal.
Acrolein Impairs the Cholesterol Transport Functions of High Density Lipoproteins
Chadwick, Alexandra C.; Holme, Rebecca L.; Chen, Yiliang; Thomas, Michael J.; Sorci-Thomas, Mary G.; Silverstein, Roy L.; Pritchard, Kirkwood A.; Sahoo, Daisy
2015-01-01
High density lipoproteins (HDL) are considered athero-protective, primarily due to their role in reverse cholesterol transport, where they transport cholesterol from peripheral tissues to the liver for excretion. The current study was designed to determine the impact of HDL modification by acrolein, a highly reactive aldehyde found in high abundance in cigarette smoke, on the cholesterol transport functions of HDL. HDL was chemically-modified with acrolein and immunoblot and mass spectrometry analyses confirmed apolipoprotein crosslinking, as well as acrolein adducts on apolipoproteins A-I and A-II. The ability of acrolein-modified HDL (acro-HDL) to serve as an acceptor of free cholesterol (FC) from COS-7 cells transiently expressing SR-BI was significantly decreased. Further, in contrast to native HDL, acro-HDL promotes higher neutral lipid accumulation in murine macrophages as judged by Oil Red O staining. The ability of acro-HDL to mediate efficient selective uptake of HDL-cholesteryl esters (CE) into SR-BI-expressing cells was reduced compared to native HDL. Together, the findings from our studies suggest that acrolein modification of HDL produces a dysfunctional particle that may ultimately promote atherogenesis by impairing functions that are critical in the reverse cholesterol transport pathway. PMID:25849485
Density functional steric analysis of linear and branched alkanes.
Ess, Daniel H; Liu, Shubin; De Proft, Frank
2010-12-16
Branched alkane hydrocarbons are thermodynamically more stable than straight-chain linear alkanes. This thermodynamic stability is also manifest in alkane bond separation energies. To understand the physical differences between branched and linear alkanes, we have utilized a novel density functional theory (DFT) definition of steric energy based on the Weizäcker kinetic energy. Using the M06-2X functional, the total DFT energy was partitioned into a steric energy term (E(s)[ρ]), an electrostatic energy term (E(e)[ρ]), and a fermionic quantum energy term (E(q)[ρ]). This analysis revealed that branched alkanes have less (destabilizing) DFT steric energy than linear alkanes. The lower steric energy of branched alkanes is mitigated by an equal and opposite quantum energy term that contains the Pauli component of the kinetic energy and exchange-correlation energy. Because the steric and quantum energy terms cancel, this leaves the electrostatic energy term that favors alkane branching. Electrostatic effects, combined with correlation energy, explains why branched alkanes are more stable than linear alkanes. PMID:21086970
Effects of Methylation on Zebularine Studied by Density Functional Theory
NASA Astrophysics Data System (ADS)
Selvam, Lalitha; Vasilyev, Vladislav; Wang, Feng; Vasilyev, Vladislav
2009-06-01
1-(β -D-ribofuranosyl)-2-pyrimidone (zebularine or zeb) and 1-(β -D-ribofuranosyl)-5-methyl-2-pyrimidinone (d5) are effective inhibitors of cytidine deaminases (CDA). Methyl modification of zeb at the C(5) position in the base moiety produces d5. A density functional theory (DFT) study reveals the impact of the methyl group on the electronic structures and spectra of the nucleoside pair. It is found that the addition of methyl group has little effect on the geometry of the nucleosides as well as their sugar puckering, but affects anisotropic properties such as dihedral angles, condensed Fukui functions and charge distribution can be seen in their molecular electrostatic potentials (MEPs). Electron spectra serve as the fingerprint for the methyl group. The valence spectra clearly indicate that the molecular pair is related in the inner valence space of IP > 20 eV, whereas the outer valence space reveals the methyl associated electronic structural modifications of the molecular pair. In the present study, the molecular orbitals (MO) such as MO8, MO18 and MO37 (HOMO as MO1) are identified as the fingerprint MOs for methyl, whereas other MOs marked in the figure are secondary methyl related MOs. Chemical shift in the inner shell and their spectra are also calculated. It reveals the similarities and differences of methyl effect to large nucleosides and small amino acids such as L-alanine.
Physical basis for constrained lattice density functional theory.
Men, Yumei; Zhang, Xianren
2012-03-28
To study nucleation phenomena in an open system, a constrained lattice density functional theory (LDFT) method has been developed before to identify the unstable directions of grand potential functional and to stabilize nuclei by imposing a suitable constraint. In this work, we answer several questions about the method on a fundamental level, and give a firmer basis for the constrained LDFT method. First, we demonstrate that the nucleus structure and free energy barrier from a volume constraint method are equivalent to those from a surface constraint method. Then, we show that for the critical nucleus, the constrained LDFT method in fact produces a bias-free solution for both the nucleus structure and nucleation barrier. Finally, we give a physical interpretation of the Lagrange multiplier in the constraint method, which provides the generalized force to stabilize a nucleus in an open system. The Lagrange multiplier is found to consist of two parts: part I of the constraint produces an effective pressure, and part II imposes a constraint to counteract the supersaturation. PMID:22462885
Self-interaction corrections in density functional theory
Tsuneda, Takao; Hirao, Kimihiko
2014-05-14
Self-interaction corrections for Kohn-Sham density functional theory are reviewed for their physical meanings, formulations, and applications. The self-interaction corrections get rid of the self-interaction error, which is the sum of the Coulomb and exchange self-interactions that remains because of the use of an approximate exchange functional. The most frequently used self-interaction correction is the Perdew-Zunger correction. However, this correction leads to instabilities in the electronic state calculations of molecules. To avoid these instabilities, several self-interaction corrections have been developed on the basis of the characteristic behaviors of self-interacting electrons, which have no two-electron interactions. These include the von Weizsäcker kinetic energy and long-range (far-from-nucleus) asymptotic correction. Applications of self-interaction corrections have shown that the self-interaction error has a serious effect on the states of core electrons, but it has a smaller than expected effect on valence electrons. This finding is supported by the fact that the distribution of self-interacting electrons indicates that they are near atomic nuclei rather than in chemical bonds.
Antisites in III-V semiconductors: Density functional theory calculations
Chroneos, A.; Tahini, H. A.; Schwingenschlögl, U.; Grimes, R. W.
2014-07-14
Density functional based simulation, corrected for finite size effects, is used to investigate systematically the formation of antisite defects in III-V semiconductors (III = Al, Ga, and In and V = P, As, and Sb). Different charge states are modelled as a function of the Fermi level and under different growth conditions. The formation energies of group III antisites (III{sub V}{sup q}) decrease with increasing covalent radius of the group V atom though not group III radius, whereas group V antisites (V{sub III}{sup q}) show a consistent decrease in formation energies with increase in group III and group V covalent radii. In general, III{sub V}{sup q} defects dominate under III-rich conditions and V{sub III}{sup q} under V-rich conditions. Comparison with equivalent vacancy formation energy simulations shows that while antisite concentrations are always dominant under stoichiometric conditions, modest variation in growth or doping conditions can lead to a significantly higher concentration of vacancies.
Metallophilic interactions from dispersion-corrected density-functional theory.
Otero-de-la-Roza, Alberto; Mallory, Joel D; Johnson, Erin R
2014-05-14
In this article, we present the first comprehensive study of metallophilic (aurophilic) interactions using dispersion-corrected density-functional theory. Dispersion interactions (an essential component of metallophilicity) are treated using the exchange-hole dipole moment (XDM) model. By comparing against coupled-cluster benchmark calculations on simple dimers, we show that LC-ωPBE-XDM is a viable functional to study interactions between closed-shell transition metals and that it performs uniformly better than second-order Møller-Plesset theory, the basic computational technique used in previous works. We apply LC-ωPBE-XDM to address several open questions regarding metallophilicity, such as the interplay between dispersion and relativistic effects, the interaction strength along group 11, the additivity of homo- and hetero-metallophilic effects, the stability of [E(AuPH3)4](+) cations (E = N, P, As, Sb), and the role of metallophilic effects in crystal packing. We find that relativistic effects explain the prevalence of aurophilicity not by stabilizing metal-metal contacts, but by preventing gold from forming ionic structures involving bridge anions (which are otherwise common for Ag and Cu) as a result of the increased electron affinity of the metal. Dispersion effects are less important than previously assumed and their stabilization contribution is relatively independent of the metal. PMID:24832312
Density Functional Steric Analysis of Linear and Branched Alkanes
Ess, Daniel H.; Liu, Shubin; De Proft, Frank
2010-11-18
Branched alkane hydrocarbons are thermodynamically more stable than straight-chain linear alkanes. This thermodynamic stability is also manifest in alkane bond separation energies. To understand the physical differences between branched and linear alkanes, we have utilized a novel density functional theory (DFT) definition of steric energy based on the Weizäcker kinetic energy. Using the M06-2X functional, the total DFT energy was partitioned into a steric energy term (E_{e}[[ρ]), an electrostatic energy term (E_{e}[ρ]), and a fermionic quantum energy term (E_{q}[[ρ]). This analysis revealed that branched alkanes have less (destabilizing) DFT steric energy than linear alkanes. The lower steric energy of branched alkanes is mitigated by an equal and opposite quantum energy term that contains the Pauli component of the kinetic energy and exchange-correlation energy. Because the steric and quantum energy terms cancel, this leaves the electrostatic energy term that favors alkane branching. Electrostatic effects, combined with correlation energy, explains why branched alkanes are more stable than linear alkanes.
Augmented Lagrangian formulation of orbital-free density functional theory
Suryanarayana, Phanish Phanish, Deepa
2014-10-15
We present an Augmented Lagrangian formulation and its real-space implementation for non-periodic Orbital-Free Density Functional Theory (OF-DFT) calculations. In particular, we rewrite the constrained minimization problem of OF-DFT as a sequence of minimization problems without any constraint, thereby making it amenable to powerful unconstrained optimization algorithms. Further, we develop a parallel implementation of this approach for the Thomas–Fermi–von Weizsacker (TFW) kinetic energy functional in the framework of higher-order finite-differences and the conjugate gradient method. With this implementation, we establish that the Augmented Lagrangian approach is highly competitive compared to the penalty and Lagrange multiplier methods. Additionally, we show that higher-order finite-differences represent a computationally efficient discretization for performing OF-DFT simulations. Overall, we demonstrate that the proposed formulation and implementation are both efficient and robust by studying selected examples, including systems consisting of thousands of atoms. We validate the accuracy of the computed energies and forces by comparing them with those obtained by existing plane-wave methods.
Drew, Simon C; Young, Charles G; Hanson, Graeme R
2007-04-01
The electron paramagnetic resonance spin Hamiltonian parameters of mononuclear thiomolybdenyl complexes based upon the tris(pyrazolyl)borate ligand, together with their molybdenyl analogues, are calculated using density functional theory. The electronic g matrix and 95Mo hyperfine matrix are calculated as second-order response properties from the coupled-perturbed Kohn-Sham equations. The scalar relativistic zero-order regular approximation (ZORA) is used with an all-electron basis and an accurate mean-field spin-orbit operator which includes all one- and two-electron terms. The principal values and relative orientations of the g and A interaction matrices obtained from the experimental spectra in a previous EPR study are compared with those obtained from unrestricted Kohn-Sham calculations at the BP86 and B3LYP level, and the latter are found to be in good quantitative agreement. A quasi-restricted approach is used to analyze the influence of the various molecular orbitals on g and A. In all complexes the ground state magnetic orbital is dX2-Y2-based and the orientation of the A matrix is directly related to the orientation of this orbital. The largest single contribution to the orientation of the g matrix arises from the spin-orbit coupling of the dYZ-based lowest-unoccupied molecular orbital into the ground state. A number of smaller, cumulative charge-transfer contributions augment the d-d contributions. A comparison of the theoretical EPR parameters obtained using both crystallographic and gas-phase geometry-optimized structures of Tp*MoO(bdt) (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate, bdt = 1,2-benzenedithiolate) suggests a correspondence between the metal-dithiolate fold angle and the angle of noncoincidence between g and A. PMID:17305330
A solvation-free-energy functional: a reference-modified density functional formulation.
Sumi, Tomonari; Mitsutake, Ayori; Maruyama, Yutaka
2015-07-01
The three-dimensional reference interaction site model (3D-RISM) theory, which is one of the most applicable integral equation theories for molecular liquids, overestimates the absolute values of solvation-free-energy (SFE) for large solute molecules in water. To improve the free-energy density functional for the SFE of solute molecules, we propose a reference-modified density functional theory (RMDFT) that is a general theoretical approach to construct the free-energy density functional systematically. In the RMDFT formulation, hard-sphere (HS) fluids are introduced as the reference system instead of an ideal polyatomic molecular gas, which has been regarded as the appropriate reference system of the interaction-site-model density functional theory for polyatomic molecular fluids. We show that using RMDFT with a reference HS system can significantly improve the absolute values of the SFE for a set of neutral amino acid side-chain analogues as well as for 504 small organic molecules. PMID:26032201
Understanding density functional theory (DFT) and completing it in practice
Bagayoko, Diola
2014-12-15
We review some salient points in the derivation of density functional theory (DFT) and of the local density approximation (LDA) of it. We then articulate an understanding of DFT and LDA that seems to be ignored in the literature. We note the well-established failures of many DFT and LDA calculations to reproduce the measured energy gaps of finite systems and band gaps of semiconductors and insulators. We then illustrate significant differences between the results from self consistent calculations using single trial basis sets and those from computations following the Bagayoko, Zhao, and Williams (BZW) method, as enhanced by Ekuma and Franklin (BZW-EF). Unlike the former, the latter calculations verifiably attain the absolute minima of the occupied energies, as required by DFT. These minima are one of the reasons for the agreement between their results and corresponding, experimental ones for the band gap and a host of other properties. Further, we note predictions of DFT BZW-EF calculations that have been confirmed by experiment. Our subsequent description of the BZW-EF method ends with the application of the Rayleigh theorem in the selection, among the several calculations the method requires, of the one whose results have a full, physics content ascribed to DFT. This application of the Rayleigh theorem adds to or completes DFT, in practice, to preserve the physical content of unoccupied, low energy levels. Discussions, including implications of the method, and a short conclusion follow the description of the method. The successive augmentation of the basis set in the BZW-EF method, needed for the application of the Rayleigh theorem, is also necessary in the search for the absolute minima of the occupied energies, in practice.
Structure and properties of cobalt clusters up to the tetramer: A density-functional study
Jamorski, C.; Martinez, A.; Castro, M.; Salahub, D.R.
1997-04-01
All-electron calculations have been performed on cobalt clusters up to the tetramer using the local and generalized gradient correction spin density formalisms. These clusters present an abundance of low-lying states. In the case of Co{sub 4}, we have found that two and three-dimensional structures are energetically very close. Symmetric structures exhibit high degeneracy. Jahn-Teller deformations have hence been investigated and have been found to play an important role in such transition-metal clusters. General trends in the magnetic moment per atom and in the attachment energy have been elucidated. {copyright} {ital 1997} {ital The American Physical Society}
NASA Astrophysics Data System (ADS)
Pham, Thinh H.; Ramprasad, Rampi; Nguyen, Huy-Viet
2016-06-01
Due to the lack of treatment of long-range dispersion energies, density functional theory with local and semilocal approximations of exchange-correlation energy is known to fail in describing van der Waals complexes, including polymer crystals. This limitation can be overcome by using a different class of functionals, called van der Waals density functional (vdW-DF), originally developed by Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)]. In this work, we performed a systematic study of structural properties of polymeric crystals using the original vdW-DF functional by Dion et al. and its variants and refinements. Our study shows that this class of functional outperforms the conventional LDA or PBE functionals and gives results with similar accuracy to that of empirical dispersion-corrected schemes such as DFT-D. This study suggests the use of vdW-DF2 functional — a revised version of vdW-DF functional — to obtain a high-fidelity prediction of structural and other properties of polymeric materials.
Pham, Thinh H; Ramprasad, Rampi; Nguyen, Huy-Viet
2016-06-01
Due to the lack of treatment of long-range dispersion energies, density functional theory with local and semilocal approximations of exchange-correlation energy is known to fail in describing van der Waals complexes, including polymer crystals. This limitation can be overcome by using a different class of functionals, called van der Waals density functional (vdW-DF), originally developed by Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)]. In this work, we performed a systematic study of structural properties of polymeric crystals using the original vdW-DF functional by Dion et al. and its variants and refinements. Our study shows that this class of functional outperforms the conventional LDA or PBE functionals and gives results with similar accuracy to that of empirical dispersion-corrected schemes such as DFT-D. This study suggests the use of vdW-DF2 functional - a revised version of vdW-DF functional - to obtain a high-fidelity prediction of structural and other properties of polymeric materials. PMID:27276968
Filtered density function approach for reactive transport in groundwater
NASA Astrophysics Data System (ADS)
Suciu, Nicolae; Schüler, Lennart; Attinger, Sabine; Knabner, Peter
2016-04-01
Spatial filtering may be used in coarse-grained simulations (CGS) of reactive transport in groundwater, similar to the large eddy simulations (LES) in turbulence. The filtered density function (FDF), stochastically equivalent to a probability density function (PDF), provides a statistical description of the sub-grid, unresolved, variability of the concentration field. Besides closing the chemical source terms in the transport equation for the mean concentration, like in LES-FDF methods, the CGS-FDF approach aims at quantifying the uncertainty over the whole hierarchy of heterogeneity scales exhibited by natural porous media. Practically, that means estimating concentration PDFs on coarse grids, at affordable computational costs. To cope with the high dimensionality of the problem in case of multi-component reactive transport and to reduce the numerical diffusion, FDF equations are solved by particle methods. But, while trajectories of computational particles are modeled as stochastic processes indexed by time, the concentration's heterogeneity is modeled as a random field, with multi-dimensional, spatio-temporal sets of indices. To overcome this conceptual inconsistency, we consider FDFs/PDFs of random species concentrations weighted by conserved scalars and we show that their evolution equations can be formulated as Fokker-Planck equations describing stochastically equivalent processes in concentration-position spaces. Numerical solutions can then be approximated by the density in the concentration-position space of an ensemble of computational particles governed by the associated Itô equations. Instead of sequential particle methods we use a global random walk (GRW) algorithm, which is stable, free of numerical diffusion, and practically insensitive to the increase of the number of particles. We illustrate the general FDF approach and the GRW numerical solution for a reduced complexity problem consisting of the transport of a single scalar in groundwater
NASA Astrophysics Data System (ADS)
Ulian, Gianfranco; Valdrè, Giovanni
2014-08-01
The knowledge of the P, T behavior of talc is very important in mineralogical-petrological and geophysical research fields because talc can be considered a hydrous phase that can recycle water into the Earth's mantle and also an important mineral in both industrial and technological applications. However, very few works have been presented to fully characterize the thermodynamic properties of this mineral, especially at atomic scale. In a previous work, we modeled the structural and mechanical properties of talc using the B3LYP-D* hybrid density functional, which included a correction for the dispersive forces and all-electron Gaussian-type orbital basis sets. The results were in good agreement with single-crystal X-ray and neutron diffraction experimental data. Here, we extend the investigation to the thermochemical and thermophysical properties of talc using the same density functional approach and the quasi-harmonic approximation, providing the thermal equation of state, the heat capacity and the entropy of the mineral at different P, T conditions.
NASA Astrophysics Data System (ADS)
Ulian, Gianfranco; Valdrè, Giovanni
2015-02-01
The knowledge of the P, T behavior of talc is very important in mineralogical-petrological and geophysical research fields because talc can be considered a hydrous phase that can recycle water into the Earth's mantle and also an important mineral in both industrial and technological applications. However, very few works have been presented to fully characterize the thermodynamic properties of this mineral, especially at atomic scale. In a previous work, we modeled the structural and mechanical properties of talc using the B3LYP-D* hybrid density functional, which included a correction for the dispersive forces and all-electron Gaussian-type orbital basis sets. The results were in good agreement with single-crystal X-ray and neutron diffraction experimental data. Here, we extend the investigation to the thermochemical and thermophysical properties of talc using the same density functional approach and the quasi-harmonic approximation, providing the thermal equation of state, the heat capacity and the entropy of the mineral at different P, T conditions.
Spin propensities of octahedral complexes from density functional theory.
Mortensen, Sara R; Kepp, Kasper P
2015-04-30
The fundamental balance between high- and low-spin states of transition metal systems depends on both the metal ion and the ligands surrounding it, as often visualized by the spectrochemical series. Most density functionals do not reproduce this balance, and real spin state propensities depend on orbital pairing and vibrational entropies absent in the spectrochemical series. Thus, we systematically computed the tendency toward high or low spin of "text-book" octahedral metal complexes versus ligand and metal type, using eight density functionals. Dispersion effects were generally <5 kJ/mol, favoring low-spin states. Zero-point energies favored high-spin states up to 33 kJ/mol for strong ligands, but down to a few kilojoules per mole for weak ligands. Vibrational entropy also favored high-spin states up to 40 kJ/mol, most for strong ligands. Jahn-Teller distortion in Co(II) low-spin states, particularly stable d(6) low-spin states, and entropy corrections were consistent with experiment. Entropy and zero-point energy corrections were markedly lower for Co(II) and Mn(III), viz., the differential ligand field stabilization energy, and can only be ignored for weak ligands. The data enable simple assessment of spin state propensities versus ligand and metal type and reveal, e.g., that CN(-) is consistently weaker than CO for M(II) but stronger than CO for M(III) and SCN(-) and NCS(-) change order in M(II) versus M(III) complexes. Contrary to expectation based on the spectrochemical series, Cl(-) and Br(-) are very close in spin state propensity because the pairing penalty for low spin is smaller in Br(-). Thus, for the M(II) complexes, we find a consensus order of Br(-) ∼ Cl(-) < H2O < SCN(-) < NCS(-) ∼ NH3 < CN(-) < CO, whereas for the M(III) complexes, an approximate order is Br(-) ∼ Cl(-) < H2O ∼ NCS(-) ∼ SCN(-)< NH3 < CO < CN(-). PMID:25856244
Wilken, F.; Bauer, D.
2006-11-17
The ionization of a one-dimensional model helium atom in short laser pulses using time-dependent density-functional theory is investigated. We calculate ionization probabilities as a function of laser intensity by approximating the correlation function of the system adiabatically with an explicit dependence on the fractional number of bound electrons. For the correlation potential we take the derivative discontinuity at integer numbers of bound electrons explicitly into account. This approach reproduces ionization probabilities from the solution of the time-dependent Schroedinger equation, in particular, the so-called knee due to nonsequential ionization.
Tensor part of the Skyrme energy density functional: Spherical nuclei
NASA Astrophysics Data System (ADS)
Lesinski, T.; Bender, M.; Bennaceur, K.; Duguet, T.; Meyer, J.
2007-07-01
the single-particle spectra in doubly-magic nuclei is deteriorated, which can be traced back to features of the single-particle spectra that are not related to the tensor terms. We conclude that the currently used central and spin-orbit parts of the Skyrme energy density functional are not flexible enough to allow for the presence of large tensor terms.
Global and local curvature in density functional theory
NASA Astrophysics Data System (ADS)
Zhao, Qing; Ioannidis, Efthymios I.; Kulik, Heather J.
2016-08-01
Piecewise linearity of the energy with respect to fractional electron removal or addition is a requirement of an electronic structure method that necessitates the presence of a derivative discontinuity at integer electron occupation. Semi-local exchange-correlation (xc) approximations within density functional theory (DFT) fail to reproduce this behavior, giving rise to deviations from linearity with a convex global curvature that is evidence of many-electron, self-interaction error and electron delocalization. Popular functional tuning strategies focus on reproducing piecewise linearity, especially to improve predictions of optical properties. In a divergent approach, Hubbard U-augmented DFT (i.e., DFT+U) treats self-interaction errors by reducing the local curvature of the energy with respect to electron removal or addition from one localized subshell to the surrounding system. Although it has been suggested that DFT+U should simultaneously alleviate global and local curvature in the atomic limit, no detailed study on real systems has been carried out to probe the validity of this statement. In this work, we show when DFT+U should minimize deviations from linearity and demonstrate that a "+U" correction will never worsen the deviation from linearity of the underlying xc approximation. However, we explain varying degrees of efficiency of the approach over 27 octahedral transition metal complexes with respect to transition metal (Sc-Cu) and ligand strength (CO, NH3, and H2O) and investigate select pathological cases where the delocalization error is invisible to DFT+U within an atomic projection framework. Finally, we demonstrate that the global and local curvatures represent different quantities that show opposing behavior with increasing ligand field strength, and we identify where these two may still coincide.
Global and local curvature in density functional theory.
Zhao, Qing; Ioannidis, Efthymios I; Kulik, Heather J
2016-08-01
Piecewise linearity of the energy with respect to fractional electron removal or addition is a requirement of an electronic structure method that necessitates the presence of a derivative discontinuity at integer electron occupation. Semi-local exchange-correlation (xc) approximations within density functional theory (DFT) fail to reproduce this behavior, giving rise to deviations from linearity with a convex global curvature that is evidence of many-electron, self-interaction error and electron delocalization. Popular functional tuning strategies focus on reproducing piecewise linearity, especially to improve predictions of optical properties. In a divergent approach, Hubbard U-augmented DFT (i.e., DFT+U) treats self-interaction errors by reducing the local curvature of the energy with respect to electron removal or addition from one localized subshell to the surrounding system. Although it has been suggested that DFT+U should simultaneously alleviate global and local curvature in the atomic limit, no detailed study on real systems has been carried out to probe the validity of this statement. In this work, we show when DFT+U should minimize deviations from linearity and demonstrate that a "+U" correction will never worsen the deviation from linearity of the underlying xc approximation. However, we explain varying degrees of efficiency of the approach over 27 octahedral transition metal complexes with respect to transition metal (Sc-Cu) and ligand strength (CO, NH3, and H2O) and investigate select pathological cases where the delocalization error is invisible to DFT+U within an atomic projection framework. Finally, we demonstrate that the global and local curvatures represent different quantities that show opposing behavior with increasing ligand field strength, and we identify where these two may still coincide. PMID:27497541
Mukamel, Shaul
2005-02-01
Time-ordered superoperators are used to develop a unified description of nonlinear density response and spontaneous fluctuations of many-electron systems. The pth-order density response functions are decomposed into 2{sup p+1} non-causal Liouville space pathways. Individual pathways are symmetric to the interchange of their space, time, and superoperator indices and can thus be calculated as functional derivatives. Other combinations of these pathways represent spontaneous density fluctuations and the response of such fluctuations to an external field. The resolution of the causality paradox of time-dependent density-functional theory (TDDFT) is shown to be intimately connected with the nonretarded nature of fluctuations.
Numerical methods for high-dimensional probability density function equations
NASA Astrophysics Data System (ADS)
Cho, H.; Venturi, D.; Karniadakis, G. E.
2016-01-01
In this paper we address the problem of computing the numerical solution to kinetic partial differential equations involving many phase variables. These types of equations arise naturally in many different areas of mathematical physics, e.g., in particle systems (Liouville and Boltzmann equations), stochastic dynamical systems (Fokker-Planck and Dostupov-Pugachev equations), random wave theory (Malakhov-Saichev equations) and coarse-grained stochastic systems (Mori-Zwanzig equations). We propose three different classes of new algorithms addressing high-dimensionality: The first one is based on separated series expansions resulting in a sequence of low-dimensional problems that can be solved recursively and in parallel by using alternating direction methods. The second class of algorithms relies on truncation of interaction in low-orders that resembles the Bogoliubov-Born-Green-Kirkwood-Yvon (BBGKY) framework of kinetic gas theory and it yields a hierarchy of coupled probability density function equations. The third class of algorithms is based on high-dimensional model representations, e.g., the ANOVA method and probabilistic collocation methods. A common feature of all these approaches is that they are reducible to the problem of computing the solution to high-dimensional equations via a sequence of low-dimensional problems. The effectiveness of the new algorithms is demonstrated in numerical examples involving nonlinear stochastic dynamical systems and partial differential equations, with up to 120 variables.
Reflection asymmetric shapes in covariant density functional theory
NASA Astrophysics Data System (ADS)
Afanasjev, A. V.; Agbemava, S.; Ring, P.
2014-03-01
Reflection asymmetric (octupole deformed) shapes play an important role in some areas of nuclear chart. For example, the outer fission barriers in actinides and superheavy nuclei are strongly affected by such shapes. The recent progress in the study of such shapes and octupole softness at ground states of lanthanides (A ~ 145) and actinides (A ~ 224) as well as at outer fission barriers of actinides and superheavy nuclei within the covariant density functional theory will be reviewed. New results obtained within the relativistic Hartree-Bogoliubov framework with separable limit of finite range Gogny D1S pairing in the pairing channel will be discussed. The experimental data will be systematically compared with model calculations. The work on the extension of the relativistic Hartree-Bogoliubov formalism to the description of odd, odd-odd and rotating nuclei with reflections asymmetric shapes is currently in progress. New results obtained with these extensions will be reported. This work has been supported by the U.S. Department of Energy under the grant DE-FG02-07ER41459 and by the DFG cluster of excellence ``Origin and Structure of the Universe '' (www.universe-cluster.de).
Parameterizing deep convection using the assumed probability density function method
Storer, R. L.; Griffin, B. M.; Hoft, Jan; Weber, J. K.; Raut, E.; Larson, Vincent E.; Wang, Minghuai; Rasch, Philip J.
2015-01-06
Due to their coarse horizontal resolution, present-day climate models must parameterize deep convection. This paper presents single-column simulations of deep convection using a probability density function (PDF) parameterization. The PDF parameterization predicts the PDF of subgrid variability of turbulence, clouds, and hydrometeors. That variability is interfaced to a prognostic microphysics scheme using a Monte Carlo sampling method.The PDF parameterization is used to simulate tropical deep convection, the transition from shallow to deep convection over land, and mid-latitude deep convection.These parameterized single-column simulations are compared with 3-D reference simulations. The agreement is satisfactory except when the convective forcing is weak. The same PDF parameterization is also used to simulate shallow cumulus and stratocumulus layers. The PDF method is sufficiently general to adequately simulate these five deep, shallow, and stratiform cloud cases with a single equation set. This raises hopes that it may be possible in the future, with further refinements at coarse time step and grid spacing, to parameterize all cloud types in a large-scale model in a unified way.
Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory
Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S.
2015-04-02
The ability to predict the equilibrium constants for the formation of 1:1 uranyl:ligand complexes (log K_{1 }values) provides the essential foundation for the rational design of ligands with enhanced uranyl affinity and selectivity. We also use density functional theory (B3LYP) and the IEFPCM continuum solvation model to compute aqueous stability constants for UO_{2}^{2+} complexes with 18 donor ligands. Theoretical calculations permit reasonably good estimates of relative binding strengths, while the absolute log K_{1} values are significantly overestimated. Accurate predictions of the absolute log K_{1} values (root mean square deviation from experiment < 1.0 for log K_{1} values ranging from 0 to 16.8) can be obtained by fitting the experimental data for two groups of mono and divalent negative oxygen donor ligands. The utility of correlations is demonstrated for amidoxime and imide dioxime ligands, providing a useful means of screening for new ligands with strong chelate capability to uranyl.
Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory
Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S.
2015-04-02
The ability to predict the equilibrium constants for the formation of 1:1 uranyl:ligand complexes (log K1 values) provides the essential foundation for the rational design of ligands with enhanced uranyl affinity and selectivity. We also use density functional theory (B3LYP) and the IEFPCM continuum solvation model to compute aqueous stability constants for UO22+ complexes with 18 donor ligands. Theoretical calculations permit reasonably good estimates of relative binding strengths, while the absolute log K1 values are significantly overestimated. Accurate predictions of the absolute log K1 values (root mean square deviation from experiment < 1.0 for log K1 values ranging from 0more » to 16.8) can be obtained by fitting the experimental data for two groups of mono and divalent negative oxygen donor ligands. The utility of correlations is demonstrated for amidoxime and imide dioxime ligands, providing a useful means of screening for new ligands with strong chelate capability to uranyl.« less
Parameterizing deep convection using the assumed probability density function method
NASA Astrophysics Data System (ADS)
Storer, R. L.; Griffin, B. M.; Höft, J.; Weber, J. K.; Raut, E.; Larson, V. E.; Wang, M.; Rasch, P. J.
2015-01-01
Due to their coarse horizontal resolution, present-day climate models must parameterize deep convection. This paper presents single-column simulations of deep convection using a probability density function (PDF) parameterization. The PDF parameterization predicts the PDF of subgrid variability of turbulence, clouds, and hydrometeors. That variability is interfaced to a prognostic microphysics scheme using a Monte Carlo sampling method. The PDF parameterization is used to simulate tropical deep convection, the transition from shallow to deep convection over land, and midlatitude deep convection. These parameterized single-column simulations are compared with 3-D reference simulations. The agreement is satisfactory except when the convective forcing is weak. The same PDF parameterization is also used to simulate shallow cumulus and stratocumulus layers. The PDF method is sufficiently general to adequately simulate these five deep, shallow, and stratiform cloud cases with a single equation set. This raises hopes that it may be possible in the future, with further refinements at coarse time step and grid spacing, to parameterize all cloud types in a large-scale model in a unified way.
Large Eddy Simulation and the Filtered Probability Density Function Method
NASA Astrophysics Data System (ADS)
Jones, W. P.; Navarro-Martinez, S.
2009-12-01
Recently there is has been increased interest in modelling combustion processes with high-levels of extinction and re-ignition. Such system often lie beyond the scope of conventional single scalar-based models. Large Eddy Simulation (LES) has shown a large potential for describing turbulent reactive systems, though combustion occurs at the smallest unresolved scales of the flow and must be modelled. In the sub-grid Probability Density Function (pdf) method approximations are devised to close the evolution equation for the joint-pdf which is then solved directly. The paper describes such an approach and concerns, in particular, the Eulerian stochastic field method of solving the pdf equation. The paper examines the capabilities of the LES-pdf method in capturing auto-ignition and extinction events in different partially premixed configurations with different fuels (hydrogen, methane and n-heptane). The results show that the LES-pdf formulation can capture different regimes without any parameter adjustments, independent of Reynolds numbers and fuel type.
Parameterizing deep convection using the assumed probability density function method
Storer, R. L.; Griffin, B. M.; Höft, J.; Weber, J. K.; Raut, E.; Larson, V. E.; Wang, M.; Rasch, P. J.
2014-06-11
Due to their coarse horizontal resolution, present-day climate models must parameterize deep convection. This paper presents single-column simulations of deep convection using a probability density function (PDF) parameterization. The PDF parameterization predicts the PDF of subgrid variability of turbulence, clouds, and hydrometeors. That variability is interfaced to a prognostic microphysics scheme using a Monte Carlo sampling method. The PDF parameterization is used to simulate tropical deep convection, the transition from shallow to deep convection over land, and mid-latitude deep convection. These parameterized single-column simulations are compared with 3-D reference simulations. The agreement is satisfactory except when the convective forcing ismore » weak. The same PDF parameterization is also used to simulate shallow cumulus and stratocumulus layers. The PDF method is sufficiently general to adequately simulate these five deep, shallow, and stratiform cloud cases with a single equation set. This raises hopes that it may be possible in the future, with further refinements at coarse time step and grid spacing, to parameterize all cloud types in a large-scale model in a unified way.« less
Parameterizing deep convection using the assumed probability density function method
Storer, R. L.; Griffin, B. M.; Höft, J.; Weber, J. K.; Raut, E.; Larson, V. E.; Wang, M.; Rasch, P. J.
2015-01-06
Due to their coarse horizontal resolution, present-day climate models must parameterize deep convection. This paper presents single-column simulations of deep convection using a probability density function (PDF) parameterization. The PDF parameterization predicts the PDF of subgrid variability of turbulence, clouds, and hydrometeors. That variability is interfaced to a prognostic microphysics scheme using a Monte Carlo sampling method. The PDF parameterization is used to simulate tropical deep convection, the transition from shallow to deep convection over land, and midlatitude deep convection. These parameterized single-column simulations are compared with 3-D reference simulations. The agreement is satisfactory except when the convective forcing ismore » weak. The same PDF parameterization is also used to simulate shallow cumulus and stratocumulus layers. The PDF method is sufficiently general to adequately simulate these five deep, shallow, and stratiform cloud cases with a single equation set. This raises hopes that it may be possible in the future, with further refinements at coarse time step and grid spacing, to parameterize all cloud types in a large-scale model in a unified way.« less
Density functional theory study of oxygen migration in molten carbonate
NASA Astrophysics Data System (ADS)
Lei, Xueling; Haines, Kahla; Huang, Kevin; Qin, Changyong
2016-02-01
The process of oxygen migration in alkali molten carbonate salts has been examined using density functional theory method. All geometries were optimized at the B3LYP/6-31G(d) level, while single point energy corrections were performed using MP4 and CCSD(T). At TS, a O-O-O linkage is formed and O-O bond forming and breaking is concerted. A cooperative "cogwheel" mechanism as described in the equation of CO42- + CO32- → CO32- ⋯O ⋯ CO32- → CO32- + CO42- is involved. The energy barrier is calculated to be 103.0, 136.3 and 127.9 kJ/mol through an intra-carbonate pathway in lithium, sodium and potassium carbonate, respectively. The reliability and accuracy of B3LYP/6-31G(d) were confirmed by CCSD(T). The calculated low values of activation energy indicate that the oxygen transfer in molten carbonate salts is fairly easy. In addition, it is found that lithium carbonate is not only a favorable molten carbonate salt for better cathode kinetics, but also it is widely used for reducing the melting point of Li/Na and Li/K eutectic MC mixtures. The current results imply that the process of oxygen reduction in MC modified cathodes is facilitated by the presence of MC, resulting in an enhancement of cell performance at low operating temperatures.
Dynamical Density Functional Theory and Hydrodynamic Interactions in Confined Systems
NASA Astrophysics Data System (ADS)
Goddard, Benjamin; Kalliadasis, Serafim; Nold, Andreas
Colloidal systems consist of nano-micrometer sized particles suspended in a bath of many more, much smaller and much lighter particles. When the colloidal particles move through the bath, e.g. when driven by external forces such as gravity, flows are induced in the bath. These flows in turn impart forces on the colloid particles. These bath-mediated forces, known as Hydrodynamic Interactions (HI) strongly influence the dynamics of the colloid particles. This is particularly true in confined systems, in which the presence of walls substantially modifies the HI compared to unbounded geometries. For many-particle systems, the number of degrees of freedom prohibit a direct solution of the underlying stochastic equations and a reduced model is necessary. We model such systems through Dynamical Density Functional Theory (DDFT), the computational complexity of which is independent of the number of particles. We include both inter-particle and particle-wall HI, demonstrating both their combined and relative effects. Funded by EPSRC Grant No. EP/L025159/1.
Efficiency issues related to probability density function comparison
Kelly, P.M.; Cannon, M.; Barros, J.E.
1996-03-01
The CANDID project (Comparison Algorithm for Navigating Digital Image Databases) employs probability density functions (PDFs) of localized feature information to represent the content of an image for search and retrieval purposes. A similarity measure between PDFs is used to identify database images that are similar to a user-provided query image. Unfortunately, signature comparison involving PDFs is a very time-consuming operation. In this paper, we look into some efficiency considerations when working with PDFS. Since PDFs can take on many forms, we look into tradeoffs between accurate representation and efficiency of manipulation for several data sets. In particular, we typically represent each PDF as a Gaussian mixture (e.g. as a weighted sum of Gaussian kernels) in the feature space. We find that by constraining all Gaussian kernels to have principal axes that are aligned to the natural axes of the feature space, computations involving these PDFs are simplified. We can also constrain the Gaussian kernels to be hyperspherical rather than hyperellipsoidal, simplifying computations even further, and yielding an order of magnitude speedup in signature comparison. This paper illustrates the tradeoffs encountered when using these constraints.
Predicting stability constants for uranyl complexes using density functional theory.
Vukovic, Sinisa; Hay, Benjamin P; Bryantsev, Vyacheslav S
2015-04-20
The ability to predict the equilibrium constants for the formation of 1:1 uranyl/ligand complexes (log K1 values) provides the essential foundation for the rational design of ligands with enhanced uranyl affinity and selectivity. We use density functional theory (B3LYP) and the integral equation formalism polarizable continuum model (IEF-PCM) to compute aqueous stability constants for UO2(2+) complexes with 18 donor ligands. Theoretical calculations permit reasonably good estimates of relative binding strengths, while the absolute log K1 values are significantly overestimated. Accurate predictions of the absolute log K1 values (root-mean-square deviation from experiment <1.0 for log K1 values ranging from 0 to 16.8) can be obtained by fitting the experimental data for two groups of mono- and divalent negative oxygen donor ligands. The utility of correlations is demonstrated for amidoxime and imide dioxime ligands, providing a useful means of screening for new ligands with strong chelating capability to uranyl. PMID:25835578
Van der Waals interactions in density functional theory
NASA Astrophysics Data System (ADS)
Langreth, David C.
2009-03-01
The van der Waals density functional which we introduced half a decade agoootnotetextM. Dion et al. Phys. Rev. Lett. 92, 246401 (2004). and its self-consistent generalizationootnotetextT. Thonhauser et al., Phys. Rev. B 76, 125112 (2007). will be briefly reviewed. There are many collaborators in the application review that will follow, not only those who worked in the physics department at Rutgers% ootnotetextMaxime Dion, Aaron Puzder, T. Thonhauser, Valentino R. Cooper, Shen Li, Eamonn Murray, Lingzhu Kong, and Kyuho Lee. and at Chalmers,% ootnotetextHenrik Rydberg, Svetla Chakarova-K"ack, Jesper Kleis, Elsebeth Schr"oder, Per Hyldgaard, and Bengt I. Lundqvist. but also at Denmarks Technical University,% ootnotetextAndrei Kelkkanen, Poul G. Moses, Jesper Kleis, and Bengt I. Lundqvist. the chemistry department at Rutgers,% ootnotetextKonhoa Li, Jing Li, Yves Chabal, and Wilma K. Olson. and most recently at the University of Texas at Dallas.% ootnotetextNour Nijem and Yves Chabal. I will expand on our recent review article,ootnotetextD. C. Langreth et al., J. Phys. Cond. Mat. (in press). which hopefully will be published before the present talk, and include applications by other groups not listed below. If possible, I will also review results from a more recent collaboration to study nucleosomal DNA and beyond.
A probability density function method for acoustic field uncertainty analysis
NASA Astrophysics Data System (ADS)
James, Kevin R.; Dowling, David R.
2005-11-01
Acoustic field predictions, whether analytical or computational, rely on knowledge of the environmental, boundary, and initial conditions. When knowledge of these conditions is uncertain, acoustic field predictions will also be uncertain, even if the techniques for field prediction are perfect. Quantifying acoustic field uncertainty is important for applications that require accurate field amplitude and phase predictions, like matched-field techniques for sonar, nondestructive evaluation, bio-medical ultrasound, and atmospheric remote sensing. Drawing on prior turbulence research, this paper describes how an evolution equation for the probability density function (PDF) of the predicted acoustic field can be derived and used to quantify predicted-acoustic-field uncertainties arising from uncertain environmental, boundary, or initial conditions. Example calculations are presented in one and two spatial dimensions for the one-point PDF for the real and imaginary parts of a harmonic field, and show that predicted field uncertainty increases with increasing range and frequency. In particular, at 500 Hz in an ideal 100 m deep underwater sound channel with a 1 m root-mean-square depth uncertainty, the PDF results presented here indicate that at a range of 5 km, all phases and a 10 dB range of amplitudes will have non-negligible probability. Evolution equations for the two-point PDF are also derived.
Time-dependent density functional theory of extreme environments
NASA Astrophysics Data System (ADS)
Shulenburger, Luke; Desjarlais, Michael; Magyar, Rudolph
2013-04-01
We describe the challenges involved when using time-dependent density functional theory (TDDFT) to describe warm dense matter (WDM) within a plane-wave, real-time formulation. WDM occurs under conditions of temperature and pressure (over 1000 K and 1 Mbar) where plasma physics meets condensed matter physics. TDDFT is especially important in this regime as it can describe ions and electrons strongly out of equilibrium. Several theoretical challenges must be overcome including assignment of initial state orbitals, choice of time-propogation scheme, treatment of PAW potentials, and inclusion of non-adiabatic effects in the potential energy surfaces. The results of these simulations are critical in several applications. For example, we will explain how the TDDFT calculation can resolve modeling inconsistencies in X-ray Thompson cross-sections, thereby improving an important temperature diagnostic in experiments. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
Density Functional Study for Homodendrimers and Amphiphilic Dendrimers.
Chen, Cangyi; Tang, Ping; Qiu, Feng; Shi, An-Chang
2016-06-23
The conformation of homodendrimers and amphiphilic dendrimers in various solvents is studied using classical density functional theory (DFT), in which the excluded-volume effects are treated explicitly. For homodendrimers in an athermal solvent, DFT results predict a remarkable fold-back behavior for the outer generation of segments, supporting the dense-core model. A coil-to-globule transition is observed for homodendrimers in a poor solvent. The size of the dendrimers, characterized by the radius of gyration, ⟨Rg⟩, is found to follow the scaling relationship, ⟨Rg⟩ ∼ N(ν), where N is the total number of segments of the dendrimers. For amphiphilic dendrimers, DFT results show that chemical modification in the outermost generation is an effective method to drive the ends toward the periphery of the dendrimers. In particular, a conformation with a hollow interior structure could be formed for amphiphilic dendrimers with longer end spacers in a selective solvent. The resulting unimolecular micelles with a hollow core and dense shell could serve as a unique candidate for encapsulation applications, such as sustained-drug-release nanocontainers. PMID:27243274
Excess electrons in ice: a density functional theory study.
Bhattacharya, Somesh Kr; Inam, Fakharul; Scandolo, Sandro
2014-02-21
We present a density functional theory study of the localization of excess electrons in the bulk and on the surface of crystalline and amorphous water ice. We analyze the initial stages of electron solvation in crystalline and amorphous ice. In the case of crystalline ice we find that excess electrons favor surface states over bulk states, even when the latter are localized at defect sites. In contrast, in amorphous ice excess electrons find it equally favorable to localize in bulk and in surface states which we attribute to the preexisting precursor states in the disordered structure. In all cases excess electrons are found to occupy the vacuum regions of the molecular network. The electron localization in the bulk of amorphous ice is assisted by its distorted hydrogen bonding network as opposed to the crystalline phase. Although qualitative, our results provide a simple interpretation of the large differences observed in the dynamics and localization of excess electrons in crystalline and amorphous ice films on metals. PMID:24401958
Simple preconditioning for time-dependent density functional perturbation theory.
Lehtovaara, Lauri; Marques, Miguel A L
2011-07-01
By far, the most common use of time-dependent density functional theory is in the linear-reponse regime, where it provides information about electronic excitations. Ideally, the linear-response equations should be solved by a method that avoids the use of the unoccupied Kohn-Sham states--such as the Sternheimer method--as this reduces the complexity and increases the precision of the calculation. However, the Sternheimer equation becomes ill-conditioned near and indefinite above the first resonant frequency, seriously hindering the use of efficient iterative solution methods. To overcome this serious limitation, and to improve the general convergence properties of the iterative techniques, we propose a simple preconditioning strategy. In our method, the Sternheimer equation is solved directly as a linear equation using an iterative Krylov subspace method, i.e., no self-consistent cycle is required. Furthermore, the preconditioner uses the information of just a few unoccupied states and requires simple and minimal modifications to existing implementations. In this way, convergence can be reached faster and in a considerably wider frequency range than the traditional approach. PMID:21744884
DENSITY-FUNCTIONAL STUDY OF THE U-ZR SYSTEM
Landa, A; Soderlind, P; Turchi, P
2008-06-25
Density-functional formalism is applied to study the phase equilibria in the U-Zr system. The obtained ground-state properties of the {gamma} (bcc) and {delta} (C32) phases are in good agreement with experimental data. The decomposition curve for the {gamma}-based U-Zr solutions is calculated. Our calculations confirm that experimentally observed 'partial' ordering of the alloy components in the {delta}-UZr{sub 2} (AlB{sub 2}) phase, in which Zr atoms occupy the 'Al' position and the two 'B' sites are randomly shared by the U and Zr atoms, is the most energetically favorable within the C32 structure. We argue that stabilization of the {delta}-UZr{sub 2} phase relative to the {alpha}-Zr (hcp) structure is due to an increase of the Zr d-band occupancy that occurs when U is alloyed with Zr. A comparison with stabilization of the {omega}-phase (also C32) in Zr under compression is made.
Density functional theory simulation of liquid helium-4 in aerogel
NASA Astrophysics Data System (ADS)
Lysogorskiy, Yu. V.; Tayurskii, D. A.
2013-10-01
The distribution of liquid 4He in different types of confinements—adsorbing and nonadsorbing aerogel on the basis of silicon dioxide SiO2 and an absorbing homogeneous strand—has been studied using the density functional theory. It has been demonstrated that the helium atoms tend to be adsorbed on the concave aerogel surface. It has been shown that, in the confinement with fractional mass dimension within certain scales, liquid helium also has a fractional mass dimension within these scales. The dependence of the energy of liquid helium on the number of atoms has been studied for different types of adsorbing surfaces. It has been established that the specific energy of liquid helium behaves differently in the cases of attractive and unattractive potentials with decreasing number of particles. This indicates that the system under consideration is nonextensive. Thus, the necessity of taking into account the surface effects and the fractional mass dimension in the studies of the properties of liquid helium in the restricted space geometry has been demonstrated.
Applications of density functional theory in materials science and engineering
NASA Astrophysics Data System (ADS)
Alvarado, Manuel, Jr.
Density Functional Theory (DFT) is a powerful tool that can be used to model various systems in materials science. Our research applies DFT to two problems of interest. First, an organic/inorganic complex dye system known as a Mayan pigment is modeled to determine chemical binding sites, verifying each model with physical data such as UV/Vis spectra. Preliminary studies on palygorskite-based mayan pigments (mayacrom blue, mayacrom purple) show excellent agreement with experimental studies when using a dimer dye geometry binding with tetrahedrally-coordinated aluminum impurity sites in palygorksite. This approach is applied to a sepiolite-based organic/inorganic dye system using thioindigo attached to a tetrahedral aluminum impurity site with an additional aluminum impurity site in close proximity to the binding site. As a second application of DFT, various grain orientations in beta-Sn are modeled under imposed strains in order to calculate elastic properties of this system. These calculations are intended to clarify discrepancies in published, experimental crystal compliance values.
Quantum Drude friction for time-dependent density functional theory
NASA Astrophysics Data System (ADS)
Neuhauser, Daniel; Lopata, Kenneth
2008-10-01
way to very simple finite grid description of scattering and multistage conductance using time-dependent density functional theory away from the linear regime, just as absorbing potentials and self-energies are useful for noninteracting systems and leads.
Assumed Probability Density Functions for Shallow and Deep Convection
NASA Astrophysics Data System (ADS)
Bogenschutz, Peter A.; Krueger, Steven K.; Khairoutdinov, Marat
2010-04-01
The assumed joint probability density function (PDF) between vertical velocity and conserved temperature and total water scalars has been suggested to be a relatively computationally inexpensive and unified subgrid-scale (SGS) parameterization for boundary layer clouds and turbulent moments. This paper analyzes the performance of five families of PDFs using large-eddy simulations of deep convection, shallow convection, and a transition from stratocumulus to trade wind cumulus. Three of the PDF families are based on the double Gaussian form and the remaining two are the single Gaussian and a Double Delta Function (analogous to a mass flux model). The assumed PDF method is tested for grid sizes as small as 0.4 km to as large as 204.8 km. In addition, studies are performed for PDF sensitivity to errors in the input moments and for how well the PDFs diagnose some higher-order moments. In general, the double Gaussian PDFs more accurately represent SGS cloud structure and turbulence moments in the boundary layer compared to the single Gaussian and Double Delta Function PDFs for the range of grid sizes tested. This is especially true for small SGS cloud fractions. While the most complex PDF, Lewellen-Yoh, better represents shallow convective cloud properties (cloud fraction and liquid water mixing ratio) compared to the less complex Analytic Double Gaussian 1 PDF, there appears to be no advantage in implementing Lewellen-Yoh for deep convection. However, the Analytic Double Gaussian 1 PDF better represents the liquid water flux, is less sensitive to errors in the input moments, and diagnoses higher order moments more accurately. Between the Lewellen-Yoh and Analytic Double Gaussian 1 PDFs, it appears that neither family is distinctly better at representing cloudy layers. However, due to the reduced computational cost and fairly robust results, it appears that the Analytic Double Gaussian 1 PDF could be an ideal family for SGS cloud and turbulence representation in coarse
Nonlocal density-functional description constructed from a correlated many-body wave function
NASA Astrophysics Data System (ADS)
Umezawa, Naoto; Tsuneyuki, Shinji
2004-03-01
We suggest a new approach to the nonlocal density-functional theory. In our method, the nonlocal correlation functional is derived from a correlated many-body wave function using the transcorrelated similarity transformation [1,2]. Our formalism is rigorous in principle if the v-representable density is assumed. In practice, Jastrow-Slater-type wave function is adopted and the correlation functional consists of many-body interactions originated from the Jastrow factor. Instead of struggling with these higher order interactions, we retain only 2-body interactions multiplying an adjusting parameter so that it can reproduce the exact correlation energy for the homogeneous electron gas. Therefore, the computational cost is comparable to the exact exchange method. Moreover, parameters in the Jastrow factor are determined by the two conditions: the cusp conditions and the random-phase approximation without empirical fitting. We found that our correlation functional gives fairly good results for small atoms and ions (He, Li^+, Be^2+, Li, and Be). [1]S. F. Boys and N. C. Handy, Proc. Roy. Soc. A, 309, 209; 310, 43; 310, 63; 311, 309. [2] N. Umezawa and S. Tsuneyuki, J. Chem. Phys. 119, 10015 (2003).
NASA Astrophysics Data System (ADS)
Klüppelberg, Daniel A.; Betzinger, Markus; Blügel, Stefan
2015-01-01
We analyze the accuracy of the atomic force within the all-electron full-potential linearized augmented plane-wave (FLAPW) method using the force formalism of Yu et al. [Phys. Rev. B 43, 6411 (1991), 10.1103/PhysRevB.43.6411]. A refinement of this formalism is presented that explicitly takes into account the tail of high-lying core states leaking out of the muffin-tin sphere and considers the small discontinuities of LAPW wave function, density, and potential at the muffin-tin sphere boundaries. For MgO and EuTiO3 it is demonstrated that these amendments substantially improve the acoustic sum rule and the symmetry of the force constant matrix. Sum rule and symmetry are realized with an accuracy of μ Htr /aB .
Surfaces of complex intermetallic compounds: insights from density functional calculations.
Hafner, Jürgen; Krajčí, Marian
2014-11-18
CONSPECTUS: Complex intermetallic compounds are a class of ordered alloys consisting of quasicrystals and other ordered compounds with large unit cells; many of them are approximant phases to quasicrystals. Quasicrystals are the limiting case where the unit cell becomes infinitely large; approximants are series of periodic structures converging to the quasicrystal. While the unique properties of quasicrystals have inspired many investigations of their surfaces, relatively little attention has been devoted to the surface properties of the approximants. In general, complex intermetallic compounds display rather irregular, often strongly corrugated surfaces, making the determination of their atomic structure a very complex and challenging task. During recent years, scanning tunneling microscopy (STM) has been used to study the surfaces of several complex intermetallic compounds. If atomic resolution can be achieved, STM permits visualization of the local atomistic surface structure. However, the interpretation of the STM images is often ambiguous and sometimes even impossible without a realistic model of the structure of the surface and the distribution of the electronic density above the surface. Here we demonstrate that ab initio density functional theory (DFT) can be used to determine the energetics and the geometric and electronic structures of the stable surfaces of complex intermetallic compounds. Calculations for surfaces with different chemical compositions can be performed in the grand canonical ensemble. Simulated cleavage experiments permit us to determine the formation of the cleavage planes requiring the lowest energy. The investigation of the adsorption of molecular species permits a comparison with temperature-programmed thermal desorption experiments. Calculated surface electronic densities of state can be compared with the results of photoelectron spectroscopy. Simulations of detailed STM images can be directly confronted with the experimental results
Fattebert, J
2008-07-29
We describe an iterative algorithm to solve electronic structure problems in Density Functional Theory. The approach is presented as a Subspace Accelerated Inexact Newton (SAIN) solver for the non-linear Kohn-Sham equations. It is related to a class of iterative algorithms known as RMM-DIIS in the electronic structure community. The method is illustrated with examples of real applications using a finite difference discretization and multigrid preconditioning.
Density functional theory and phytochemical study of Pistagremic acid
NASA Astrophysics Data System (ADS)
Ullah, Habib; Rauf, Abdur; Ullah, Zakir; Fazl-i-Sattar; Anwar, Muhammad; Shah, Anwar-ul-Haq Ali; Uddin, Ghias; Ayub, Khurshid
2014-01-01
We report here for the first time a comparative theoretical and experimental study of Pistagremic acid (P.A). We have developed a theoretical model for obtaining the electronic and spectroscopic properties of P.A. The simulated data showed nice correlation with the experimental data. The geometric and electronic properties were simulated at B3LYP/6-31 G (d, p) level of density functional theory (DFT). The optimized geometric parameters of P.A were found consistent with those from X-ray crystal structure. Differences of about 0.01 and 0.15 Å in bond length and 0.19-1.30° degree in the angles, respectively; were observed between the experimental and theoretical data. The theoretical vibrational bands of P.A were found to correlate with the experimental IR spectrum after a common scaling factor of 0.963. The experimental and predicted UV-Vis spectra (at B3LYP/6-31+G (d, p)) have 36 nm differences. This difference from experimental results is because of the condensed phase nature of P.A. Electronic properties such as Ionization Potential (I.P), Electron Affinities (E.A), co-efficient of highest occupied molecular orbital (HOMO), co-efficient of lowest unoccupied molecular orbital (LUMO) of P.A were estimated for the first time however, no correlation can be made with experiment. Inter-molecular interaction and its effect on vibrational (IR), electronic and geometric parameters were simulated by using Formic acid as model for hydrogen bonding in P.A.
Density functional study of condensation in capped capillaries.
Yatsyshin, P; Savva, N; Kalliadasis, S
2015-07-15
We study liquid adsorption in narrow rectangular capped capillaries formed by capping two parallel planar walls (a slit pore) with a third wall orthogonal to the two planar walls. The most important transition in confined fluids is arguably condensation, where the pore becomes filled with the liquid phase which is metastable in the bulk. Depending on the temperature T, the condensation in capped capillaries can be first-order (at T≤Tcw) or continuous (at T>Tcw), where Tcw is the capillary wetting temperature. At T>Tcw, the capping wall can adsorb mesoscopic amounts of metastable under-condensed liquid. The onset of condensation is then manifested by the continuous unbinding of the interface between the liquid adsorbed on the capping wall and the gas filling the rest of the capillary volume. In wide capped capillaries there may be a remnant of wedge filling transition, which is manifested by the adsorption of liquid drops in the corners. Our classical statistical mechanical treatment predicts a possibility of three-phase coexistence between gas, corner drops and liquid slabs adsorbed on the capping wall. In sufficiently wide capillaries we find that thick prewetting films of finite length may be nucleated at the capping wall below the boundary of the prewetting transition. Prewetting then proceeds in a continuous manner manifested by the unbinding interface between the thick and thin films adsorbed on the side walls. Our analysis is based on a detailed numerical investigation of the density functional theory for the fluid equilibria for a number of illustrative case studies. PMID:26086161
Density functional study of condensation in capped capillaries
NASA Astrophysics Data System (ADS)
Yatsyshin, P.; Savva, N.; Kalliadasis, S.
2015-07-01
We study liquid adsorption in narrow rectangular capped capillaries formed by capping two parallel planar walls (a slit pore) with a third wall orthogonal to the two planar walls. The most important transition in confined fluids is arguably condensation, where the pore becomes filled with the liquid phase which is metastable in the bulk. Depending on the temperature T, the condensation in capped capillaries can be first-order (at T≤slant {{T}\\text{cw}} ) or continuous (at T\\gt {{T}\\text{cw}} ), where {{T}\\text{cw}} is the capillary wetting temperature. At T \\gt {{T}\\text{cw}} , the capping wall can adsorb mesoscopic amounts of metastable under-condensed liquid. The onset of condensation is then manifested by the continuous unbinding of the interface between the liquid adsorbed on the capping wall and the gas filling the rest of the capillary volume. In wide capped capillaries there may be a remnant of wedge filling transition, which is manifested by the adsorption of liquid drops in the corners. Our classical statistical mechanical treatment predicts a possibility of three-phase coexistence between gas, corner drops and liquid slabs adsorbed on the capping wall. In sufficiently wide capillaries we find that thick prewetting films of finite length may be nucleated at the capping wall below the boundary of the prewetting transition. Prewetting then proceeds in a continuous manner manifested by the unbinding interface between the thick and thin films adsorbed on the side walls. Our analysis is based on a detailed numerical investigation of the density functional theory for the fluid equilibria for a number of illustrative case studies.
Density functional theory study of neutral and oxidized thiophene oligomers
NASA Astrophysics Data System (ADS)
Dai, Yafei; Wei, Chengwei; Blaisten-Barojas, Estela
2013-11-01
The effect of oxidation on the energetics and structure of thiophene (Th) oligomers is studied with density functional theory at the B3PW91/6-311++G(d,p) level. Neutral n-Th oligomers (2 < n < 13) are gently curved planar chains. Ionization potential and electron affinity results show that n-Th oligomers are easier to be oxidized as their chain length increases. Oxidation states +2, +4, +6, and +8 are energetically stable in 12-Th. Upon oxidation the conjugated backbone of 12-Th switches from extended benzenoid phase to quinoid phase localized on groups of monomers regularly spaced along the chain. Oxidized states +2, +4, +6, and +8 of 12-Th display two +1e localized at the ends of their chains only because of the finite size of the chains. In 12-Th this end-effect extends over the two terminal monomers forming a positive-negative charge duet. This peculiar charge localization makes n-Th oligomers different from other conducting polymers with similar structure, such as polypyrrole. The spectrum of single-electron molecular states of oxidized 12-Th displays two localized single-electron states in the HOMO-LUMO energy gap per +2 oxidation state. Oligothiophene 12-Th doped with F atoms at 1:2 concentration presents a charge transfer of 3.4 e from oligomer to dopants that increases to 4.8 e in the presence of solvent. The charge distribution in these F-doped oligomers is similar to the +4 oxidation state of 12-Th. It is predicted that dopants produce an enhanced charge transfer localized in the proximity of their locations enhancing the formation of bipolarons in the central part of the oligomer chain.
Density functional theory and phytochemical study of Pistagremic acid.
Ullah, Habib; Rauf, Abdur; Ullah, Zakir; Fazl-i-Sattar; Anwar, Muhammad; Shah, Anwar-ul-Haq Ali; Uddin, Ghias; Ayub, Khurshid
2014-01-24
We report here for the first time a comparative theoretical and experimental study of Pistagremic acid (P.A). We have developed a theoretical model for obtaining the electronic and spectroscopic properties of P.A. The simulated data showed nice correlation with the experimental data. The geometric and electronic properties were simulated at B3LYP/6-31 G (d, p) level of density functional theory (DFT). The optimized geometric parameters of P.A were found consistent with those from X-ray crystal structure. Differences of about 0.01 and 0.15 Å in bond length and 0.19-1.30° degree in the angles, respectively; were observed between the experimental and theoretical data. The theoretical vibrational bands of P.A were found to correlate with the experimental IR spectrum after a common scaling factor of 0.963. The experimental and predicted UV-Vis spectra (at B3LYP/6-31+G (d, p)) have 36 nm differences. This difference from experimental results is because of the condensed phase nature of P.A. Electronic properties such as Ionization Potential (I.P), Electron Affinities (E.A), co-efficient of highest occupied molecular orbital (HOMO), co-efficient of lowest unoccupied molecular orbital (LUMO) of P.A were estimated for the first time however, no correlation can be made with experiment. Inter-molecular interaction and its effect on vibrational (IR), electronic and geometric parameters were simulated by using Formic acid as model for hydrogen bonding in P.A. PMID:24051292
Density Functional Theory applied to magnetic materials: Mn3O4 at different hybrid functionals
NASA Astrophysics Data System (ADS)
Ribeiro, R. A. P.; de Lazaro, S. R.; Pianaro, S. A.
2015-10-01
Antiferromagnetic Mn3O4 in spinel structure was investigated employing the Density Functional Theory at different hybrid functionals with default HF exchange percentage. Structural, electronic and magnetic properties were examined. Structural results were in agreement with experimental and Hartree-Fock results showing that the octahedral site was distorted by the Jahn-Teller effect, which changed the electron density distribution. Band-gap results for B3LYP and B3PW hybrid functionals were closer to the experimental when compared to PBE0. Mulliken Population Analysis revealed magnetic moments very close to ideal d4 and d5 electron configurations of Mn3+ and Mn2+, respectively. Electron density maps are useful to determine that oxygen atoms mediate the electron transfer between octahedral and tetrahedral clusters. Magnetic properties were investigated from theoretical results for exchange coupling constants. Intratetrahedral and tetra-octahedral interactions were observed to be antiferromagnetic, whereas, octahedral sites presented antiferromagnetic interactions in the same layer and ferromagnetic in adjacent layers. Results showed that only default B3LYP was successful to describe magnetic properties of antiferromagnetic materials in agreement with experimental results.
NASA Astrophysics Data System (ADS)
Putaja, A.; Eich, F. G.; Baldsiefen, T.; Räsänen, E.
2016-03-01
Physically valid and numerically efficient approximations for the exchange and correlation energy are critical for reduced-density-matrix-functional theory to become a widely used method in electronic structure calculations. Here we examine the physical limits of power functionals of the form f (n ,n') =(nn')α for the scaling function in the exchange-correlation energy. To this end we obtain numerically the minimizing momentum distributions for the three- and two-dimensional homogeneous electron gas, respectively. In particular, we examine the limiting values for the power α to yield physically sound solutions that satisfy the Lieb-Oxford lower bound for the exchange-correlation energy and exclude pinned states with the condition n (k )<1 for all wave vectors k . The results refine the constraints previously obtained from trial momentum distributions. We also compute the values for α that yield the exact correlation energy and its kinetic part for both the three- and two-dimensional electron gas. In both systems, narrow regimes of validity and accuracy are found at α ≳0.6 and at rs≳10 for the density parameter, corresponding to relatively low densities.
Symmetry Energy as a Function of Density and Mass
Danielewicz, Pawel; Lee, Jenny
2007-10-26
Energy in nuclear matter is, in practice, completely characterized at different densities and asymmetries, when the density dependencies of symmetry energy and of energy of symmetric matter are specified. The density dependence of the symmetry energy at subnormal densities produces mass dependence of nuclear symmetry coefficient and, thus, can be constrained by that latter dependence. We deduce values of the mass dependent symmetry coefficients, by using excitation energies to isobaric analog states. The coefficient systematic, for intermediate and high masses, is well described in terms of the symmetry coefficient values of a{sub a}{sup V} = (31.5-33.5) MeV for the volume coefficient and a{sub a}{sup S} = (9-12) MeV for the surface coefficient. These two further correspond to the parameter values describing density dependence of symmetry energy, of L{approx}95 MeV and K{sub sym}{approx}25 MeV.
Density functional theory modeling of multilayer "epitaxial" graphene oxide.
Zhou, Si; Bongiorno, Angelo
2014-11-18
CONSPECTUS: Graphene oxide (GO) is a complex material of both fundamental and applied interest. Elucidating the structure of GO is crucial to achieve control over its properties and technological applications. GO is a nonstoichiometric and hygroscopic material with a lamellar structure, and its physical chemical properties depend critically on synthesis procedures and postsynthesis treatments. Numerous efforts are in place to both understand and exploit this versatile layered carbon material. This Account reports on recent density functional theory (DFT) studies of "epitaxial" graphene oxide (hereafter EGO), a type of GO obtained by oxidation of graphene films grown epitaxially on silicon carbide. Here, we rely on selected X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR), and X-ray diffraction (XRD) measurements of EGO, and we discuss in great detail how we utilized DFT-based techniques to project out from the experimental data basic atomistic information about the chemistry and structure of these films. This Account provides an example as to how DFT modeling can be used to elucidate complex materials such as GO from a limited set of experimental information. EGO exhibits a uniform layered structure, consisting of a stack of graphene planes hosting predominantly epoxide and hydroxyl groups, and water molecules intercalated between the oxidized carbon layers. Here, we first focus on XPS measurements of EGO, and we use DFT to generate realistic model structures, calculate core-level chemical shifts, and through the comparison with experiment, gain insight on the chemical composition and metastability characteristics of EGO. DFT calculations are then used to devise a simplistic but accurate simulation scheme to study thermodynamic and kinetic stability and to predict the intralayer structure of EGO films aged at room temperature. Our simulations show that aged EGO encompasses layers with nanosized oxidized domains presenting a high concentration of
Laser Spectroscopy and Density Functional Study on Niobium Dimer Cation
NASA Astrophysics Data System (ADS)
Aydin, Metin; Lombardi, John R.
2009-06-01
Resonant multiphoton fragmentation spectra of niobium dimer cation (Nb2+) have been obtained by utilizing laser vaporization of a Nb metal target. Ions are mass-selected with a time-of-flight mass spectrometer followed by a mass gate, then fragmented with a pulsed dye laser, and the resulting fragment ions are detected with a second time-of-flight reflectron mass spectrometer and multichannel plate. Photon resonances are detected by monitoring ion current as a function of fragmentation laser wavelength. A rich, but complex spectrum of the cation is obtained. The bands display a characteristic multiplet structure that may be interpreted as due to transitions from the ground state X^{4}{Σ}^{-}({Ω}g) to several excited states, X^{4}{Π}({Ω}u) and X^{4}{Σ}(^{-}{Ω}u). The ground state X^{4}{Σ}^{-}({Ω}g) is derived from the electron configuration ({π}{_u})^{4} (1{σ}{_g})^{2}(2{σ}{_g})^{1} ({δ}{_g})^{2}. The two spin-orbit components are split by 145 cm^{-1} due to a strong second-order isoconfigurational spin-orbit interaction with the low-lying ^{2}{Σ}^{+}({Ω}g) state. The vibrational frequencies of the ground sate and the excited state of Nb2+ are identified as well as molecular spin-orbit constants (A{_S}{_O}) in the excited state. The electronic structure of niobium dimer cation was investigated using density functional theory. For the electronic ground state, the predicted spectroscopic properties were in good agreement with experiment. Calculations on excited states reveal congested manifolds of quartet and doublet electronic states in the range 0-30,000 cm^{-1}, reflecting the multitude of possible electronic promotions among the 4d- and 5s-based molecular orbitals. Comparisons are drawn between Nb^{+}{_2} and the prevalent isoelectronic molecules V^{+}{_2}/NbV^{+}/Nb{_2}/V{_2}/NbV. M. Aydin and John R. Lombardi J. Phys. Chem. A. xx XXXX 2009.
Density functional study on the functionalization of BN nanotubes with nitramide
NASA Astrophysics Data System (ADS)
Kakemam, Jamal; Noei, M.
2014-10-01
Chemical functionalization of a boron nitride nanotube (BNNT) with nitramide molecule (H2NNO2) has been investigated using density functional theory. It was found that the molecule prefers to be adsorbed and dissociated on a diagonal B-N bond of the tube surface so that the -NH2 and -NO2 groups are attached on B and N atoms, releasing energy of 0.50 eV. The results show that the functionalized BNNT is more soluble than the pristine one which may render the chemical modification process to be an effective way for purification of the BNNTs. Depending on the cleavage behavior of nitramide on the tube, HOMO/LUMO gap of the system can be either decreased or increased while the chemically modified BNNT is still a semiconductor. Furthermore, the chemical functionalization results in hindered field emission in the tube by raising the potential barrier of the electron emission.
NASA Astrophysics Data System (ADS)
Mattsson, Ann E.; Wills, John M.
2013-03-01
The inability to computationally describe the physics governing the properties of actinides and their alloys is the poster child of failure of existing Density Functional Theory exchange-correlation functionals. The intricate competition between localization and delocalization of the electrons, present in these materials, exposes the limitations of functionals only designed to properly describe one or the other situation. We will discuss the manifestation of this competition in real materials and propositions on how to construct a functional able to accurately describe properties of these materials. I addition we will discuss both the importance of using the Dirac equation to describe the relativistic effects in these materials, and the connection to the physics of transition metal oxides. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
NASA Astrophysics Data System (ADS)
Marana, Naiara L.; Albuquerque, Anderson R.; La Porta, Felipe A.; Longo, Elson; Sambrano, Julio R.
2016-05-01
Periodic density functional theory calculations with the B3LYP hybrid functional and all-electron Gaussian basis set were performed to simulate the structural and electronic properties as well as the strain and formation energies of single-walled ZnO nanotubes (SWZnONTs) and Carbon nanotubes (SWCNTs) with different chiralities as functions of their diameters. For all SWZnONTs, the band gap, strain energy, and formation energy converge to ~4.5 eV, 0.0 eV/atom, and 0.40 eV/atom, respectively. This result suggests that the nanotubes are formed more easily from the surface than from the bulk. For SWCNTs, the strain energy is always positive, while the formation energy is negative for armchair and zigzag nanotubes, therefore suggesting that these types of nanotubes can be preferentially formed from the bulk. The electronic properties of SWCNTs depend on the chirality; all armchair nanotubes are metallic, while zigzag and chiral nanotubes can be metallic or semiconducting, depending on the n and m vectors.
NASA Astrophysics Data System (ADS)
Dove, P. M.; Wallace, A. F.; Gibbs, G. V.
2007-12-01
The dissolution of amorphous and crystalline varieties of SiO2 is an integral part of the global biogeochemical cycle of silicon. Nanoparticulate biogenic silica produced by marine phytoplankton and terrestrial plants are of particular interest because their enhanced reactivity and abundance make them important sources and sinks of dissolved silicon in natural environments. Recent experimental results on (100) surfaces of quartz show that the dominant dissolution mechanism in simple H2O solutions is by retreat of Q2 groups along step edges. In the presence of electrolytes, rates are accelerated by up to 100X in the presence by a crossover in the dominant dissolution mechanism to nucleation of vacancy islands at Q3 terminated species (Dove et al., PNAS, 2005). While the control of surface coordination in reactivity is clear, the molecular pathway by which electrolytes induce dissolution by a nucleated process remains poorly understood. The results of previous ab initio investigations of Si-O bond hydrolysis by water have demonstrated that the reaction proceeds through the dissociative adsorption of H2O at the silica surface, resulting in the formation of a pentacoordinated Si transition state, followed by the transfer of one of the water bound hydrogen atoms to a bridging oxygen in the SiO2 bonded network, and breakage of the Si-O bond. Assuming a similar reaction path, the specific effects of hydrated group II metal cations (Mg2+, Ca2+, Sr2+, Ba2+) on the energetics of Si-O bond hydrolysis have been investigated with density functional methods (B3LYP) and a relatively large neutral silica cluster (H8Si6O16). Reactant, product, and transition states for Q3 to Q2 hydrolysis in the presence and absence of the afore-mentioned cations have been determined with all electron (6-31G(d)) and effective core potential (SDDALL) Gaussian basis sets. The free energy of activation for Q3 to Q2 Si-O bond hydrolysis was determined to be approximately 5 kJ/mol lower for Ca2+ than Mg
Nishimoto, Yoshio
2015-09-07
We develop a formalism for the calculation of excitation energies and excited state gradients for the self-consistent-charge density-functional tight-binding method with the third-order contributions of a Taylor series of the density functional theory energy with respect to the fluctuation of electron density (time-dependent density-functional tight-binding (TD-DFTB3)). The formulation of the excitation energy is based on the existing time-dependent density functional theory and the older TD-DFTB2 formulae. The analytical gradient is computed by solving Z-vector equations, and it requires one to calculate the third-order derivative of the total energy with respect to density matrix elements due to the inclusion of the third-order contributions. The comparison of adiabatic excitation energies for selected small and medium-size molecules using the TD-DFTB2 and TD-DFTB3 methods shows that the inclusion of the third-order contributions does not affect excitation energies significantly. A different set of parameters, which are optimized for DFTB3, slightly improves the prediction of adiabatic excitation energies statistically. The application of TD-DFTB for the prediction of absorption and fluorescence energies of cresyl violet demonstrates that TD-DFTB3 reproduced the experimental fluorescence energy quite well.
Nishimoto, Yoshio
2015-09-01
We develop a formalism for the calculation of excitation energies and excited state gradients for the self-consistent-charge density-functional tight-binding method with the third-order contributions of a Taylor series of the density functional theory energy with respect to the fluctuation of electron density (time-dependent density-functional tight-binding (TD-DFTB3)). The formulation of the excitation energy is based on the existing time-dependent density functional theory and the older TD-DFTB2 formulae. The analytical gradient is computed by solving Z-vector equations, and it requires one to calculate the third-order derivative of the total energy with respect to density matrix elements due to the inclusion of the third-order contributions. The comparison of adiabatic excitation energies for selected small and medium-size molecules using the TD-DFTB2 and TD-DFTB3 methods shows that the inclusion of the third-order contributions does not affect excitation energies significantly. A different set of parameters, which are optimized for DFTB3, slightly improves the prediction of adiabatic excitation energies statistically. The application of TD-DFTB for the prediction of absorption and fluorescence energies of cresyl violet demonstrates that TD-DFTB3 reproduced the experimental fluorescence energy quite well. PMID:26342360
Exact density functional and wave function embedding schemes based on orbital localization
NASA Astrophysics Data System (ADS)
Hégely, Bence; Nagy, Péter R.; Ferenczy, György G.; Kállay, Mihály
2016-08-01
Exact schemes for the embedding of density functional theory (DFT) and wave function theory (WFT) methods into lower-level DFT or WFT approaches are introduced utilizing orbital localization. First, a simple modification of the projector-based embedding scheme of Manby and co-workers [J. Chem. Phys. 140, 18A507 (2014)] is proposed. We also use localized orbitals to partition the system, but instead of augmenting the Fock operator with a somewhat arbitrary level-shift projector we solve the Huzinaga-equation, which strictly enforces the Pauli exclusion principle. Second, the embedding of WFT methods in local correlation approaches is studied. Since the latter methods split up the system into local domains, very simple embedding theories can be defined if the domains of the active subsystem and the environment are treated at a different level. The considered embedding schemes are benchmarked for reaction energies and compared to quantum mechanics (QM)/molecular mechanics (MM) and vacuum embedding. We conclude that for DFT-in-DFT embedding, the Huzinaga-equation-based scheme is more efficient than the other approaches, but QM/MM or even simple vacuum embedding is still competitive in particular cases. Concerning the embedding of wave function methods, the clear winner is the embedding of WFT into low-level local correlation approaches, and WFT-in-DFT embedding can only be more advantageous if a non-hybrid density functional is employed.
Modeling the Pauli potential in the pair density functional theory.
Amovilli, C; Nagy, A
2008-11-28
In the ground state the pair density can be determined by solving a single auxiliary equation of a two-particle problem. A novel method for determining the Pauli potential entering this equation is presented and, starting from a reliable description of the pair density, an analytical expression is derived for atomic systems. Test calculations are presented for Be and isoelectronic C(2+) and O(4+) ions. PMID:19045853
Density Functional Theory Calculations of Mass Transport in UO2
Andersson, Anders D.; Dorado, Boris; Uberuaga, Blas P.; Stanek, Christopher R.
2012-06-26
In this talk we present results of density functional theory (DFT) calculations of U, O and fission gas diffusion in UO{sub 2}. These processes all impact nuclear fuel performance. For example, the formation and retention of fission gas bubbles induce fuel swelling, which leads to mechanical interaction with the clad thereby increasing the probability for clad breach. Alternatively, fission gas can be released from the fuel to the plenum, which increases the pressure on the clad walls and decreases the gap thermal conductivity. The evolution of fuel microstructure features is strongly coupled to diffusion of U vacancies. Since both U and fission gas transport rates vary strongly with the O stoichiometry, it is also important to understand O diffusion. In order to better understand bulk Xe behavior in UO{sub 2{+-}x} we first calculate the relevant activation energies using DFT techniques. By analyzing a combination of Xe solution thermodynamics, migration barriers and the interaction of dissolved Xe atoms with U, we demonstrate that Xe diffusion predominantly occurs via a vacancy-mediated mechanism. Since Xe transport is closely related to diffusion of U vacancies, we have also studied the activation energy for this process. In order to explain the low value of 2.4 eV found for U migration from independent damage experiments (not thermal equilibrium) the presence of vacancy clusters must be included in the analysis. Next we investigate species transport on the (111) UO{sub 2} surface, which is motivated by the formation of small voids partially filled with fission gas atoms (bubbles) in UO{sub 2} under irradiation. Surface diffusion could be the rate-limiting step for diffusion of such bubbles, which is an alternative mechanism for mass transport in these materials. As expected, the activation energy for surface diffusion is significantly lower than for bulk transport. These results are further discussed in terms of engineering-scale fission gas release models
Zinc surface complexes on birnessite: A density functional theory study
Kwon, Kideok D.; Refson, Keith; Sposito, Garrison
2009-01-05
Biogeochemical cycling of zinc is strongly influenced by sorption on birnessite minerals (layer-type MnO2), which are found in diverse terrestrial and aquatic environments. Zinc has been observed to form both tetrahedral (Zn{sup IV}) and octahedral (Zn{sup VI}) triple-corner-sharing surface complexes (TCS) at Mn(IV) vacancy sites in hexagonal birnessite. The octahedral complex is expected to be similar to that of Zn in the Mn oxide mineral, chalcophanite (ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O), but the reason for the occurrence of the four-coordinate Zn surface species remains unclear. We address this issue computationally using spin-polarized Density Functional Theory (DFT) to examine the Zn{sub IV}-TCS and Zn{sup VI}-TCS species. Structural parameters obtained by DFT geometry optimization were in excellent agreement with available experimental data on Zn-birnessites. Total energy, magnetic moments, and electron-overlap populations obtained by DFT for isolated Zn{sup IV}-TCS revealed that this species is stable in birnessite without a need for Mn(III) substitution in the octahedral sheet and that it is more effective in reducing undersaturation of surface O at a Mn vacancy than is Zn{sub VI}-TCS. Comparison between geometry-optimized ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O (chalcophanite) and the hypothetical monohydrate mineral, ZnMn{sub 3}O{sub 7} {center_dot} H{sub 2}O, which contains only tetrahedral Zn, showed that the hydration state of Zn significantly affects birnessite structural stability. Finally, our study also revealed that, relative to their positions in an ideal vacancy-free MnO{sub 2}, Mn nearest to Zn in a TCS surface complex move toward the vacancy by 0.08-0.11 {angstrom}, while surface O bordering the vacancy move away from it by 0.16-0.21 {angstrom}, in agreement with recent X-ray absorption spectroscopic analyses.
Native defects in oxide semiconductors: a density functional approach.
Oba, Fumiyasu; Choi, Minseok; Togo, Atsushi; Seko, Atsuto; Tanaka, Isao
2010-09-29
We report a semilocal and hybrid Hartree-Fock density functional study of native defects in three oxide semiconductors: ZnO, SrTiO(3), and SnO. The defect that is responsible for the n-type conductivity of ZnO has been debated, in which the O vacancy, Zn interstitial, their complexes, and residual H impurity are considered candidates. Our results indicate that the O vacancy induces a deep and localized in-gap state, whereas the Zn interstitial is a shallow donor and hence can be a source of the carriers. In view of the formation energies, the O vacancy is likely to form with a substantial concentration under O-poor conditions, but the Zn interstitial is unlikely. We thus propose that the O vacancy is relevant to the nonstoichiometry of ZnO and that a source other than the native defects, such as the H impurity, needs to be considered for the n-type conductivity. For SrTiO(3), the O vacancy and its complexes have been regarded as the origins of some of the remarkable electrical and optical properties. We suggest significant roles of the Ti antisite for a new insight into the defect-induced properties. Two types of Ti antisite, both of which are off-centered from the Sr site but toward different directions, exhibit low formation energies under Ti-rich conditions as does the O vacancy. They can explain optical properties such as visible-light emission, deep-level absorption, and the ferroelectricity observed in reduced SrTiO(3). As an example of p-type conductors, SnO has been investigated with a focus on the acceptor-like native defects. Under O-rich conditions, the Sn vacancy and O interstitial are found to be energetically favorable. The Sn vacancy induces shallow acceptor levels and can therefore be a source of carriers. The O interstitial shows no in-gap levels and hence it is inactive in terms of the carrier generation and compensation. However, this defect is a key to the understanding of the structures of intermediate compounds between SnO and SnO(2). PMID
Probability density functions for use when calculating standardised drought indices
NASA Astrophysics Data System (ADS)
Svensson, Cecilia; Prosdocimi, Ilaria; Hannaford, Jamie
2015-04-01
Time series of drought indices like the standardised precipitation index (SPI) and standardised flow index (SFI) require a statistical probability density function to be fitted to the observed (generally monthly) precipitation and river flow data. Once fitted, the quantiles are transformed to a Normal distribution with mean = 0 and standard deviation = 1. These transformed data are the SPI/SFI, which are widely used in drought studies, including for drought monitoring and early warning applications. Different distributions were fitted to rainfall and river flow data accumulated over 1, 3, 6 and 12 months for 121 catchments in the United Kingdom. These catchments represent a range of catchment characteristics in a mid-latitude climate. Both rainfall and river flow data have a lower bound at 0, as rains and flows cannot be negative. Their empirical distributions also tend to have positive skewness, and therefore the Gamma distribution has often been a natural and suitable choice for describing the data statistically. However, after transformation of the data to Normal distributions to obtain the SPIs and SFIs for the 121 catchments, the distributions are rejected in 11% and 19% of cases, respectively, by the Shapiro-Wilk test. Three-parameter distributions traditionally used in hydrological applications, such as the Pearson type 3 for rainfall and the Generalised Logistic and Generalised Extreme Value distributions for river flow, tend to make the transformed data fit better, with rejection rates of 5% or less. However, none of these three-parameter distributions have a lower bound at zero. This means that the lower tail of the fitted distribution may potentially go below zero, which would result in a lower limit to the calculated SPI and SFI values (as observations can never reach into this lower tail of the theoretical distribution). The Tweedie distribution can overcome the problems found when using either the Gamma or the above three-parameter distributions. The
NASA Astrophysics Data System (ADS)
Tachikawa, Hiroto; Iyama, Tetsuji; Kawabata, Hiroshi
2016-05-01
Electronic structures and formation mechanism of hydrogen functionalized carbon nanotube (CNT) have been investigated by means of density functional theory (DFT) method. The mechanism of hydrogen addition reaction to the CNT surface was also investigated. Pure and boron-nitrogen (BN) substituted CNT (denoted by CNT and BN-CNT, respectively) were examined as the carbon nanotubes. It was found that the additions of hydrogen atom to B (boron atom) and C (carbon atom) sites of BN-CNT proceed without activation barrier, whereas the hydrogenation of N (nitrogen atom) site needs the activation energy. The electronic states of hydrogen functionalized CNT and BN-CNT were discussed on the basis of theoretical results.
Sundararajan, Mahesh; Sinha, Vivek; Bandyopadhyay, Tusar; Ghosh, Swapan K
2012-05-01
The feasibility of using cucurbituril host molecule as a probable actinyl cation binders candidate is investigated through density functional theory based calculations. Various possible binding sites of the cucurbit[5]uril host molecule to uranyl are analyzed and based on the binding energy evaluations, μ(5)-binding is predicted to be favored. For this coordination, the structure, vibrational spectra, and binding energies are evaluated for the binding of three actinyls in hexa-valent and penta-valent oxidation states with functionalized cucurbiturils. Functionalizing cucurbituril with methyl and cyclohexyl groups increases the binding affinities of actinyls, whereas fluorination decreases the binding affinities as compared to the native host molecule. Surprisingly hydroxylation of the host molecule does not distinguish the oxidation state of the three actinyls. PMID:22471316
LIBXC: A library of exchange and correlation functionals for density functional theory
NASA Astrophysics Data System (ADS)
Marques, Miguel A. L.; Oliveira, Micael J. T.; Burnus, Tobias
2012-10-01
The central quantity of density functional theory is the so-called exchange-correlation functional. This quantity encompasses all non-trivial many-body effects of the ground-state and has to be approximated in any practical application of the theory. For the past 50 years, hundreds of such approximations have appeared, with many successfully persisting in the electronic structure community and literature. Here, we present a library that contains routines to evaluate many of these functionals (around 180) and their derivatives. Program summary Program title: LIBXC Catalogue identifier: AEMU_v1_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AEMU_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU Lesser General Public License version 3 No. of lines in distributed program, including test data, etc.: 87455 No. of bytes in distributed program, including test data, etc.: 945365 Distribution format: tar.gz Programming language: C with Fortran bindings. Computer: All. Operating system: All. RAM: N.A. Classification: 7.3, 16.1. Nature of problem: Evaluation of the exchange-correlation energy functional and its derivatives. This is a fundamental part of any atomic, molecular, or solid-state code that uses density-functional theory. Solution method: The values of the energy functional and its derivatives are given in a real grid of mesh points. Running time: Typically much smaller than the remainder of the electronic structure code. The running time has a natural linear scaling with the number of grid points.
Density Dependent Functional Forms Drive Compensation in Populations Exposed to Stressors
The interaction between density dependence (DD) and environmental stressors can result in a compensatory or synergistic response in population growth, and population models that use density-independent demographic rates or generic DD functions may be introducing bias into managem...
Reimers, Jeffrey R; Solomon, Gemma C; Gagliardi, Alessio; Bilić, Ante; Hush, Noel S; Frauenheim, Thomas; Di Carlo, Aldo; Pecchia, Alessandro
2007-07-01
A review is presented of the nonequilibrium Green's function (NEGF) method "gDFTB" for evaluating elastic and inelastic conduction through single molecules employing the density functional tight-binding (DFTB) electronic structure method. This focuses on the possible advantages that DFTB implementations of NEGF have over conventional methods based on density functional theory, including not only the ability to treat large irregular metal-molecule junctions with high nonequilibrium thermal distributions but perhaps also the ability to treat dispersive forces, bond breakage, and open-shell systems and to avoid large band lineup errors. New results are presented indicating that DFTB provides a useful depiction of simple gold-thiol interactions. Symmetry is implemented in DFTB, and the advantages it brings in terms of large savings of computational resources with significant increase in numerical stability are described. The power of DFTB is then harnessed to allow the use of gDFTB as a real-time tool to discover the nature of the forces that control inelastic charge transport through molecules and the role of molecular symmetry in determining both elastic and inelastic transport. Future directions for the development of the method are discussed. PMID:17530826
The computational foundations of time dependent density functional theory
NASA Astrophysics Data System (ADS)
Whitfield, James
2014-03-01
The mathematical foundations of TDDFT are established through the formal existence of a fictitious non-interacting system (known as the Kohn-Sham system), which can reproduce the one-electron reduced probability density of the actual system. We build upon these works and show that on the interior of the domain of existence, the Kohn-Sham system can be efficiently obtained given the time-dependent density. Since a quantum computer can efficiently produce such time-dependent densities, we present a polynomial time quantum algorithm to generate the time-dependent Kohn-Sham potential with controllable error bounds. Further, we find that systems do not immediately become non-representable but rather become ill-representable as one approaches this boundary. A representability parameter is defined in our work which quantifies the distance to the boundary of representability and the computational difficulty of finding the Kohn-Sham system.
Fattebert, J.-L.
2010-01-20
An Accelerated Block Preconditioned Gradient (ABPG) method is proposed to solve electronic structure problems in Density Functional Theory. This iterative algorithm is designed to solve directly the non-linear Kohn-Sham equations for accurate discretization schemes involving a large number of degrees of freedom. It makes use of an acceleration scheme similar to what is known as RMM-DIIS in the electronic structure community. The method is illustrated with examples of convergence for large scale applications using a finite difference discretization and multigrid preconditioning.
Kohn-Sham density-functional theory and renormalization of many-body perturbation expansions
NASA Astrophysics Data System (ADS)
Valiev, Marat
1998-03-01
Numerous practical applications provide strong evidence that despite its simplicity and crude approximations, density-functional theory leads to a rather accurate description of ground state properties of various condensed matter systems. Although well documented numerically, to our knowledge a theoretical explanation of the accuracy of density-functional theory has not been given. This issue is clarified in this work by demonstrating that density-functional theory represents a particular renormalization procedure of a many-body perturbation expansion. In other words, it is shown that density-functional theory is a many-body perturbation theory whose convergence properties have been optimized. The realization of this fact brings new meaning into density-functional theory and explains the success of density-functional based calculations. For more information go to http://alchemy.ucsd.edu/marat/ .
Patching the Exchange-Correlation Potential in Density Functional Theory.
Huang, Chen
2016-05-10
A method for directly patching exchange-correlation (XC) potentials in materials is derived. The electron density of a system is partitioned into subsystem densities by dividing its Kohn-Sham (KS) potential among the subsystems. Inside each subsystem, its projected KS potential is required to become the total system's KS potential. This requirement, together with the nearsightedness principle of electronic matters, ensures that the electronic structures inside subsystems can be good approximations to the total system's electronic structure. The nearsightedness principle also ensures that subsystem densities could be well localized in their regions, making it possible to use high-level methods to invert the XC potentials for subsystem densities. Two XC patching methods are developed. In the local XC patching method, the total system's XC potential is improved in the cluster region. We show that the coupling between a cluster and its environment is important for achieving a fast convergence of the electronic structure in the cluster region. In the global XC patching method, we discuss how to patch the subsystem XC potentials to construct the XC potential in the total system, aiming to scale up high-level quantum mechanics simulations of materials. Proof-of-principle examples are given. PMID:27049843
Stretched hydrogen molecule from a constrained-search density-functional perspective
Valone, Steven M; Levy, Mel
2009-01-01
Constrained-search density functional theory gives valuable insights into the fundamentals of density functional theory. It provides exact results and bounds on the ground- and excited-state density functionals. An important advantage of the theory is that it gives guidance in the construction of functionals. Here they engage constrained search theory to explore issues associated with the functional behavior of 'stretched bonds' in molecular hydrogen. A constrained search is performed with familiar valence bond wavefunctions ordinarily used to describe molecular hydrogen. The effective, one-electron hamiltonian is computed and compared to the corresponding uncorrelated, Hartree-Fock effective hamiltonian. Analysis of the functional suggests the need to construct different functionals for the same density and to allow a competition among these functions. As a result the correlation energy functional is composed explicitly of energy gaps from the different functionals.
Probability density function of a passive scalar in turbulent shear flows
Kollmann, W.; Janicka, J.
1982-10-01
The transport equation for the probability density function of a scalar in turbulent shear flow is analyzed and the closure based on the gradient flux model for the turbulent flux and an integral model for the scalar dissipation term is put forward. The probability density function equation is complemented by a two-equation turbulence model. Application to several shear flows proves the capability of the closure model to determine the probability density function of passive scalars.
NASA Astrophysics Data System (ADS)
Ranjbar, Ahmad; Khazaei, Mohammad; Venkataramanan, Natarajan Sathiyamoorthy; Lee, Hoonkyung; Kawazoe, Yoshiyuki
2011-03-01
Using first-principles density functional theory, we investigated the hydrogen storage capacity of Li-functionalized adamantane. We showed that if one of the acidic hydrogen atoms of adamantane is replaced by Li/Li+, the resulting complex is activated and ready to adsorb hydrogen molecules at a high gravimetric weight percent of around ~7.0%. Due to polarization of hydrogen molecules under the induced electric field generated by positively charged Li/Li+, they are adsorbed on ADM.Li/Li+ complexes with an average binding energy of ~-0.15 eV/H2, desirable for hydrogen storage applications. We also examined the possibility of the replacement of a larger number of acidic hydrogen atoms of adamantane by Li/Li+ and the possibility of aggregations of formed complexes in experiments. The stability of the proposed structures was investigated by calculating vibrational spectra and doing MD simulations.
Electronic states of alkyl-radical-functionalized C20 fullerene using density functional theory
NASA Astrophysics Data System (ADS)
Abe, Shigeaki; Kawano, Shimpei; Toida, Yu; Nakamura, Mariko; Inoue, Satoshi; Sano, Hidehiko; Yoshida, Yasuhiro; Kawabata, Hiroshi; Tachikawa, Hiroto
2016-03-01
The structures and electronic states of alkyl-radical-functionalized C20 fullerenes (denoted by C20-R) have been investigated using density functional theory (DFT). The different alkyl radicals investigated were methyl, ethyl, propyl, and butyl radicals. The DFT calculation indicated that the alkyl radical binds to the carbon atom of C20 in the on-top site, thus forming a strong C-C single bond. The binding energies of the alkyl radicals to C20 were calculated to be 83.9-86.6 kcal/mol at the CAM-B3LYP/6-311G(d,p) level. The electronic states of the C20-R complex are discussed on the basis of the theoretical results.
A simple weighted-density-functional approach to the structure of inhomogeneous fluids
NASA Astrophysics Data System (ADS)
Patra, Chandra N.; Ghosh, Swapan K.
2002-05-01
A simple weighted-density-functional approach is developed for inhomogeneous fluids by approximating the excess free energy density functional by that of the corresponding uniform system evaluated at an effective density. This effective weighted density is obtained by a suitable local averaging procedure of the actual density distribution using a weight function which is evaluated only once at the bulk density, thus being decoupled from the weighted density. This approach does not involve any power series expansion or solution of any nonlinear differential equation at every point and each iteration, as is required in some of the analogous schemes. The new theory is applied to predict the structure of simple classical fluids, interacting with hard sphere, Coulombic as well as Yukawa potentials, under confinement in several geometries. The calculated results on the density profiles are shown to compare quite well with available simulation data.
Fixed-sample optimization using a probability density function
Barnett, R.N.; Sun, Zhiwei; Lester, W.A. Jr. |
1997-12-31
We consider the problem of optimizing parameters in a trial function that is to be used in fixed-node diffusion Monte Carlo calculations. We employ a trial function with a Boys-Handy correlation function and a one-particle basis set of high quality. By employing sample points picked from a positive definite distribution, parameters that determine the nodes of the trial function can be varied without introducing singularities into the optimization. For CH as a test system, we find that a trial function of high quality is obtained and that this trial function yields an improved fixed-node energy. This result sheds light on the important question of how to improve the nodal structure and, thereby, the accuracy of diffusion Monte Carlo.
Norm-conserving pseudopotentials with chemical accuracy compared to all-electron calculations
NASA Astrophysics Data System (ADS)
Willand, Alex; Kvashnin, Yaroslav O.; Genovese, Luigi; Vázquez-Mayagoitia, Álvaro; Deb, Arpan Krishna; Sadeghi, Ali; Deutsch, Thierry; Goedecker, Stefan
2013-03-01
By adding a nonlinear core correction to the well established dual space Gaussian type pseudopotentials for the chemical elements up to the third period, we construct improved pseudopotentials for the Perdew-Burke-Ernzerhof [J. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996), 10.1103/PhysRevLett.77.3865] functional and demonstrate that they exhibit excellent accuracy. Our benchmarks for the G2-1 test set show average atomization energy errors of only half a kcal/mol. The pseudopotentials also remain highly reliable for high pressure phases of crystalline solids. When supplemented by empirical dispersion corrections [S. Grimme, J. Comput. Chem. 27, 1787 (2006), 10.1002/jcc.20495; S. Grimme, J. Antony, S. Ehrlich, and H. Krieg, J. Chem. Phys. 132, 154104 (2010), 10.1063/1.3382344] the average error in the interaction energy between molecules is also about half a kcal/mol. The accuracy that can be obtained by these pseudopotentials in combination with a systematic basis set is well superior to the accuracy that can be obtained by commonly used medium size Gaussian basis sets in all-electron calculations.
Local thermodynamic mapping for effective liquid density-functional theory
NASA Technical Reports Server (NTRS)
Kyrlidis, Agathagelos; Brown, Robert A.
1992-01-01
The structural-mapping approximation introduced by Lutsko and Baus (1990) in the generalized effective-liquid approximation is extended to include a local thermodynamic mapping based on a spatially dependent effective density for approximating the solid phase in terms of the uniform liquid. This latter approximation, called the local generalized effective-liquid approximation (LGELA) yields excellent predictions for the free energy of hard-sphere solids and for the conditions of coexistence of a hard-sphere fcc solid with a liquid. Moreover, the predicted free energy remains single valued for calculations with more loosely packed crystalline structures, such as the diamond lattice. The spatial dependence of the weighted density makes the LGELA useful in the study of inhomogeneous solids.
NASA Astrophysics Data System (ADS)
Xia, Junchao; Carter, Emily A.
2015-01-01
We present a comprehensive study of single-point kinetic energy density functionals (KEDFs) to be used in orbital-free density functional theory (DFT) calculations. We first propose a form of KEDFs based on a pointwise Kohn-Sham (KS) kinetic energy density (KED) and electron localization function (ELF) analysis. We find that the ELF and modified enhancement factor have a very strong and transferable correlation with the reduced density in various bulk metals. The non-self-consistent kinetic energy errors predicted by our KEDF models are decreased greatly compared to previously reported generalized gradient approximation (GGA) KEDFs. Second, we perform self-consistent calculations with various single-point KEDFs and investigate their numerical convergence behavior. We find striking numerical instabilities for previous GGA KEDFs; most of the GGA KEDFs fail to converge and show unphysical densities during the optimization. In contrast, our KEDFs demonstrate stable convergence, and their self-consistent results of various bulk properties agree reasonably well with KSDFT. A further detailed KED analysis reveals an interesting bifurcation phenomenon in defective metals and alloys, which may shed light on directions for future KEDF development.
NASA Astrophysics Data System (ADS)
Odkhuu, Dorj; Seok Yun, Won; Cheol Hong, Soon
2012-03-01
To understand the negligible magnetostriction of Fe-Si alloys used as cores in electric transformers or motors, density-functional calculations were performed on the tetragonal magnetostriction coefficient, λ001, of Fe1-xSix (x ≤ 0.25) alloys as a function of x using the highly precise all-electron full-potential linearized augmented plane-wave method. It was found that the calculated magnetostriction coefficients closely reproduced experimental trends and the negligible magnetostriction near x = 0.111 originated from the mixed phases of A2, B2, and D03; each different atomic type of Fe of Fe0.889Si0.111 has a small and opposite contribution to the magnetostriction.
Electronic states of aryl radical functionalized graphenes: Density functional theory study
NASA Astrophysics Data System (ADS)
Tachikawa, Hiroto; Kawabata, Hiroshi
2016-06-01
Functionalized graphenes are known as a high-performance molecular device. In the present study, the structures and electronic states of the aryl radical functionalized graphene have been investigated by the density functional theory (DFT) method to elucidate the effects of functionalization on the electronic states of graphene (GR). Also, the mechanism of aryl radical reaction with GR was investigated. The benzene, biphenyl, p-terphenyl, and p-quaterphenyl radicals [denoted by (Bz) n (n = 1–4), where n means numbers of benzene rings in aryl radical] were examined as aryl radicals. The DFT calculation of GR–(Bz) n (n = 1–4) showed that the aryl radical binds to the carbon atom of GR, and a C–C single bond was formed. The binding energies of aryl radicals to GR were calculated to be ca. 6.0 kcal mol‑1 at the CAM-B3LYP/6-311G(d,p) level. It was found that the activation barrier exists in the aryl radical addition: the barrier heights were calculated to be 10.0 kcal mol‑1. The electronic states of GR–(Bz) n were examined on the basis of theoretical results.
Chemical functionalization of graphene by carbene cycloaddition: A density functional theory study
NASA Astrophysics Data System (ADS)
Zan, Wenyan
2014-08-01
In this work, we have systematically studied the structural, energetic and electronic properties of graphene functionalized with carbene groups by using density functional theory. Introducing a low concentration of CCl2 group in graphene was studied in detail by DFT, and closed cyclopropane-like three-membered ring structure was formed, meanwhile, the potential candidate carbene groups CR2 (R = H, F, CH3, CN, NO2, OCH3, CCH, C6H5) were added to graphene sheet, and CR2 (R = H, NO2, CH3) groups were expected to be good reactive species to covalently modify graphene. The graphene functionalization with carbene groups above can open graphene's band gap. More CCl2 molecules were added to graphene, and different concentrations of CCl2 group can tune graphene's band gap. In addition, the addition of CCl2 group to graphene edges was investigated, and the stronger binding energy was found. Multiple CCl2 molecules preferred to be bound with the same edge of graphene nanoribbon. This work provides an insight into the detailed molecular mechanism of graphene functionalization with carbene groups.
Functionalization of silicon carbide nanotube by dichlorocarbene: A density functional theory study
NASA Astrophysics Data System (ADS)
Xiao, Bo; Hu, Hong; Zhao, Jing-xiang; Ding, Yi-hong
2014-02-01
The existence of numerous unsaturated π bonds on surface of nanotubes is hopeful for effective chemical functionalization. Recently, the dichlorocarbene (CCl2)-functionalization has been widely applied to modify the electronic properties of carbon nanotubes (CNTs) and boron nitride nanotubes (BNNTs), through a simple one-step formation of the open three-membered-ring (3MR) structure. Here using density functional theory methods, we study the CCl2-functionalization of silicon carbide nanotubes (SiCNTs). Three distinct sequential steps are identified as: (1) 3MR formation, (2) Cl shift from C to Si atom, and (3) C bridging between a Si-C bond. Since the initial 3MR-formation is notably exothermic (2.47 eV), the subsequent steps take place easily, leading to the eventual adjacent C2 formation in the alternative C-Si network. Clearly, the adsorption behavior of CCl2 on SiCNTs contrasts sharply to that on CNTs and BNNTs, where the open 3MR structure is the eventually stabilized state with the two C-Cl bonds intactness. Such effective C-Cl splitting significantly decreases the band gap of SiCNT by about 50%. The adsorption of more CCl2 molecules leads to a transition from semiconducting SiCNT to degenerated p-type semiconducting SiCNT. The present results not only testify the high surface chemical reactivity of SiCNT, but also show a new way of tuning the electronic properties of SiCNT.
McKechnie, Scott; Booth, George H.; Cohen, Aron J.; Cole, Jacqueline M.
2015-05-21
The best practice in computational methods for determining vertical ionization energies (VIEs) is assessed, via reference to experimentally determined VIEs that are corroborated by highly accurate coupled-cluster calculations. These reference values are used to benchmark the performance of density functional theory (DFT) and wave function methods: Hartree-Fock theory, second-order Møller-Plesset perturbation theory, and Electron Propagator Theory (EPT). The core test set consists of 147 small molecules. An extended set of six larger molecules, from benzene to hexacene, is also considered to investigate the dependence of the results on molecule size. The closest agreement with experiment is found for ionization energies obtained from total energy difference calculations. In particular, DFT calculations using exchange-correlation functionals with either a large amount of exact exchange or long-range correction perform best. The results from these functionals are also the least sensitive to an increase in molecule size. In general, ionization energies calculated directly from the orbital energies of the neutral species are less accurate and more sensitive to an increase in molecule size. For the single-calculation approach, the EPT calculations are in closest agreement for both sets of molecules. For the orbital energies from DFT functionals, only those with long-range correction give quantitative agreement with dramatic failing for all other functionals considered. The results offer a practical hierarchy of approximations for the calculation of vertical ionization energies. In addition, the experimental and computational reference values can be used as a standardized set of benchmarks, against which other approximate methods can be compared.
McKechnie, Scott; Booth, George H; Cohen, Aron J; Cole, Jacqueline M
2015-05-21
The best practice in computational methods for determining vertical ionization energies (VIEs) is assessed, via reference to experimentally determined VIEs that are corroborated by highly accurate coupled-cluster calculations. These reference values are used to benchmark the performance of density functional theory (DFT) and wave function methods: Hartree-Fock theory, second-order Møller-Plesset perturbation theory, and Electron Propagator Theory (EPT). The core test set consists of 147 small molecules. An extended set of six larger molecules, from benzene to hexacene, is also considered to investigate the dependence of the results on molecule size. The closest agreement with experiment is found for ionization energies obtained from total energy difference calculations. In particular, DFT calculations using exchange-correlation functionals with either a large amount of exact exchange or long-range correction perform best. The results from these functionals are also the least sensitive to an increase in molecule size. In general, ionization energies calculated directly from the orbital energies of the neutral species are less accurate and more sensitive to an increase in molecule size. For the single-calculation approach, the EPT calculations are in closest agreement for both sets of molecules. For the orbital energies from DFT functionals, only those with long-range correction give quantitative agreement with dramatic failing for all other functionals considered. The results offer a practical hierarchy of approximations for the calculation of vertical ionization energies. In addition, the experimental and computational reference values can be used as a standardized set of benchmarks, against which other approximate methods can be compared. PMID:26001454
Element orbitals for Kohn-Sham density functional theory
Lin, Lin; Ying, Lexing
2012-05-08
We present a method to discretize the Kohn-Sham Hamiltonian matrix in the pseudopotential framework by a small set of basis functions automatically contracted from a uniform basis set such as planewaves. Each basis function is localized around an element, which is a small part of the global domain containing multiple atoms. We demonstrate that the resulting basis set achieves meV accuracy for 3D densely packed systems with a small number of basis functions per atom. The procedure is applicable to insulating and metallic systems.
Morzan, Uriel N.; Ramírez, Francisco F.; Scherlis, Damián A. E-mail: mcgl@qb.ffyb.uba.ar; Lebrero, Mariano C. González E-mail: mcgl@qb.ffyb.uba.ar
2014-04-28
This article presents a time dependent density functional theory (TDDFT) implementation to propagate the Kohn-Sham equations in real time, including the effects of a molecular environment through a Quantum-Mechanics Molecular-Mechanics (QM-MM) hamiltonian. The code delivers an all-electron description employing Gaussian basis functions, and incorporates the Amber force-field in the QM-MM treatment. The most expensive parts of the computation, comprising the commutators between the hamiltonian and the density matrix—required to propagate the electron dynamics—, and the evaluation of the exchange-correlation energy, were migrated to the CUDA platform to run on graphics processing units, which remarkably accelerates the performance of the code. The method was validated by reproducing linear-response TDDFT results for the absorption spectra of several molecular species. Two different schemes were tested to propagate the quantum dynamics: (i) a leap-frog Verlet algorithm, and (ii) the Magnus expansion to first-order. These two approaches were confronted, to find that the Magnus scheme is more efficient by a factor of six in small molecules. Interestingly, the presence of iron was found to seriously limitate the length of the integration time step, due to the high frequencies associated with the core-electrons. This highlights the importance of pseudopotentials to alleviate the cost of the propagation of the inner states when heavy nuclei are present. Finally, the methodology was applied to investigate the shifts induced by the chemical environment on the most intense UV absorption bands of two model systems of general relevance: the formamide molecule in water solution, and the carboxy-heme group in Flavohemoglobin. In both cases, shifts of several nanometers are observed, consistently with the available experimental data.
NASA Astrophysics Data System (ADS)
Morzan, Uriel N.; Ramírez, Francisco F.; Oviedo, M. Belén; Sánchez, Cristián G.; Scherlis, Damián A.; Lebrero, Mariano C. González
2014-04-01
This article presents a time dependent density functional theory (TDDFT) implementation to propagate the Kohn-Sham equations in real time, including the effects of a molecular environment through a Quantum-Mechanics Molecular-Mechanics (QM-MM) hamiltonian. The code delivers an all-electron description employing Gaussian basis functions, and incorporates the Amber force-field in the QM-MM treatment. The most expensive parts of the computation, comprising the commutators between the hamiltonian and the density matrix—required to propagate the electron dynamics—, and the evaluation of the exchange-correlation energy, were migrated to the CUDA platform to run on graphics processing units, which remarkably accelerates the performance of the code. The method was validated by reproducing linear-response TDDFT results for the absorption spectra of several molecular species. Two different schemes were tested to propagate the quantum dynamics: (i) a leap-frog Verlet algorithm, and (ii) the Magnus expansion to first-order. These two approaches were confronted, to find that the Magnus scheme is more efficient by a factor of six in small molecules. Interestingly, the presence of iron was found to seriously limitate the length of the integration time step, due to the high frequencies associated with the core-electrons. This highlights the importance of pseudopotentials to alleviate the cost of the propagation of the inner states when heavy nuclei are present. Finally, the methodology was applied to investigate the shifts induced by the chemical environment on the most intense UV absorption bands of two model systems of general relevance: the formamide molecule in water solution, and the carboxy-heme group in Flavohemoglobin. In both cases, shifts of several nanometers are observed, consistently with the available experimental data.
NASA Astrophysics Data System (ADS)
Wang, Yang; Stocks, G. Malcolm
Under extreme conditions of temperature and pressure, interatomic separations in condensed matter can approach a small fraction of those under normal laboratory conditions. For example, during high-energy (~ 100 keV) radiation damage cascades, interatomic separations can be as small as 0.5Å. Under such conditions, core states between neighboring atoms could overlap and must be included as band states. Here we use Green's function method in the framework of multiple scattering theory, also known as Korringa-Kohn-Rostoker (KKR) electronic structure methods, to seamlessly integrate these core overlap effects within an all-electron ab initio approach. To accomplish these we use multiple integration contours in the complex plane that incorporate states normally treated as bound atomic levels. We show results for Ni and NiFe alloys in extreme densities (a /a0 ~ 0 . 3) to illustrate the convergence of the method with respect to which core states are banded as well as the angular moment cut-off required to establish absolute convergence of the total energies. Results are compared with those of plane-wave methods for different choices of the underlying pseudo potential to establish the range of validity of the various approaches.
Density Functional Theory (dft) Simulations of Shocked Liquid Xenon
NASA Astrophysics Data System (ADS)
Mattsson, Thomas R.; Magyar, Rudolph J.
2009-12-01
Xenon is not only a technologically important element used in laser technologies and jet propulsion, but it is also one of the most accessible materials in which to study the metal-insulator transition with increasing pressure. Because of its closed shell electronic configuration, xenon is often assumed to be chemically inert, interacting almost entirely through the van der Waals interaction, and at liquid density, is typically modeled well using Leonard-Jones potentials. However, such modeling has a limited range of validity as xenon is known to form compounds under normal conditions and likely exhibits considerably more chemistry at higher densities when hybridization of occupied orbitals becomes significant. We present DFT-MD simulations of shocked liquid xenon with the goal of developing an improved equation of state. The calculated Hugoniot to 2 MPa compares well with available experimental shock data. Sandia is a mul-tiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
Density Functional Theory (DFT) Simulations of Shocked Liquid Xenon
NASA Astrophysics Data System (ADS)
Mattsson, Thomas R.; Magyar, Rudolph J.
2009-06-01
Xenon is not only a technologically important element used in laser technologies and jet propulsion, but it is also one of the most accessible materials in which to study the metal-insulator transition with increasing pressure. Because of its closed shell electronic configuration, Xenon is often assumed to be chemically inert, interacting almost entirely through the van der Waals interaction, and at liquid density, is typically modeled well using Leonard-Jones potentials. However, such modeling has a limited range of validity as Xenon is known to form compounds at normal conditions and likely exhibits considerably more chemistry at higher densities when hybridization of occupied orbitals becomes significant. In this talk, we present DFT-MD simulations of shocked liquid Xenon with the goal of developing an improved equation of state. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
A Variational Framework for Spectral Approximations of Kohn-Sham Density Functional Theory
NASA Astrophysics Data System (ADS)
Wang, Xin-Cindy; Blesgen, Thomas; Bhattacharya, Kaushik; Ortiz, Michael
2016-08-01
We reformulate the Kohn-Sham density functional theory (KSDFT) as a nested variational problem in the one-particle density operator, the electrostatic potential and a field dual to the electron density. The corresponding functional is linear in the density operator and thus amenable to spectral representation. Based on this reformulation, we introduce a new approximation scheme, termed spectral binning, which does not require smoothing of the occupancy function and thus applies at arbitrarily low temperatures. We prove convergence of the approximate solutions with respect to spectral binning and with respect to an additional spatial discretization of the domain.
Goel, Himanshu; Butler, Charles L; Windom, Zachary W; Rai, Neeraj
2016-07-12
Recent developments in dispersion corrected and nonlocal density functionals are aimed at accurately capturing dispersion interactions, a key shortcoming of local and semilocal approximations of density functional theory. These functionals have shown significant promise for dimers and small clusters of molecules as well as crystalline materials. However, their efficacy for predicting vapor liquid equilibria is largely unexplored. In this work, we examine the accuracy of dispersion-corrected and nonlocal van der Waals functionals by computing the vapor liquid coexistence curves (VLCCs) of hydrofluoromethanes. Our results indicate that the PBE-D3 functional performs significantly better in predicting saturated liquid densities than the rVV10 functional. With the PBE-D3 functional, we also find that as the number of fluorine atoms increase in the molecule, the accuracy of saturated liquid density prediction improves as well. All the functionals significantly underpredict the saturated vapor densities, which also result in an underprediction of saturated vapor pressure of all compounds. Despite the differences in the bulk liquid densities, the local microstructures of the liquid CFH3 and CF2H2 are relatively insensitive to the density functional employed. For CF3H, however, rVV10 predicts slightly more structured liquid than the PBE-D3 functional. PMID:27295451
NASA Astrophysics Data System (ADS)
Solovyeva, Alisa; Pavanello, Michele; Neugebauer, Johannes
2012-05-01
Subsystem density-functional theory (DFT) is a powerful and efficient alternative to Kohn-Sham DFT for large systems composed of several weakly interacting subunits. Here, we provide a systematic investigation of the spin-density distributions obtained in subsystem DFT calculations for radicals in explicit environments. This includes a small radical in a solvent shell, a π-stacked guanine-thymine radical cation, and a benchmark application to a model for the special pair radical cation, which is a dimer of bacteriochlorophyll pigments, from the photosynthetic reaction center of purple bacteria. We investigate the differences in the spin densities resulting from subsystem DFT and Kohn-Sham DFT calculations. In these comparisons, we focus on the problem of overdelocalization of spin densities due to the self-interaction error in DFT. It is demonstrated that subsystem DFT can reduce this problem, while it still allows to describe spin-polarization effects crossing the boundaries of the subsystems. In practical calculations of spin densities for radicals in a given environment, it may thus be a pragmatic alternative to Kohn-Sham DFT calculations. In our calculation on the special pair radical cation, we show that the coordinating histidine residues reduce the spin-density asymmetry between the two halves of this system, while inclusion of a larger binding pocket model increases this asymmetry. The unidirectional energy transfer in photosynthetic reaction centers is related to the asymmetry introduced by the protein environment.
Solovyeva, Alisa; Pavanello, Michele; Neugebauer, Johannes
2012-05-21
Subsystem density-functional theory (DFT) is a powerful and efficient alternative to Kohn-Sham DFT for large systems composed of several weakly interacting subunits. Here, we provide a systematic investigation of the spin-density distributions obtained in subsystem DFT calculations for radicals in explicit environments. This includes a small radical in a solvent shell, a {pi}-stacked guanine-thymine radical cation, and a benchmark application to a model for the special pair radical cation, which is a dimer of bacteriochlorophyll pigments, from the photosynthetic reaction center of purple bacteria. We investigate the differences in the spin densities resulting from subsystem DFT and Kohn-Sham DFT calculations. In these comparisons, we focus on the problem of overdelocalization of spin densities due to the self-interaction error in DFT. It is demonstrated that subsystem DFT can reduce this problem, while it still allows to describe spin-polarization effects crossing the boundaries of the subsystems. In practical calculations of spin densities for radicals in a given environment, it may thus be a pragmatic alternative to Kohn-Sham DFT calculations. In our calculation on the special pair radical cation, we show that the coordinating histidine residues reduce the spin-density asymmetry between the two halves of this system, while inclusion of a larger binding pocket model increases this asymmetry. The unidirectional energy transfer in photosynthetic reaction centers is related to the asymmetry introduced by the protein environment.
Transverse spin gradient functional for non-collinear Spin Density Functional Theory
NASA Astrophysics Data System (ADS)
Eich, F. G.; Vignale, G.; Gross, E. K. U.
2013-03-01
The ab-initio description of non-collinear magnetism is essential for the search of new materials suitable for the construction of spintronic devices. We present a novel functional explicitly constructed for the description of non-collinear magnetism. It is formulated in terms of a Spin Gradient Extension (SGE) to the Local Spin Density Approximation, which introduces a dependence on the transverse gradients of the spin magnetization. While collinear Generalized Gradient Approximations provide a dependence on longitudinal spin gradients the SGE takes into account that longitudinal and transverse variations of the spin magnetization affect the energy differently. The explicit dependence on the transverse gradients is obtained from a reference systems which exhibits non-collinearity, i.e., the spin-spiral-wave state of the uniform electron gas. The inclusion of transverse spin gradients yields exchange-correlation magnetic fields that are non-collinear w.r.t. the spin magnetization. This implies that the spin-current density of the Kohn-Sham system does not vanish even if no external magnetic field is applied. As an example we present the application of the SGE to the non-collinear 120°-Néel state of a Chromium mono-layer. F.G.E. is supported by DOE grant No. DE-FG02-05ER46203
Harbola, Upendra; Mukamel, Shaul
2004-11-01
Electrostatic and dispersive interactions of polarizable molecules are expressed in terms of generalized (nonretarded) charge-density response functions of the isolated molecules, which in turn are expanded using the collective electronic oscillator (CEO) eigenmodes of linearized time-dependent density-functional theory. Closed expressions for the intermolecular energy are derived to sixth order in charge fluctuation amplitudes.
Afanasjev, A. V.
2015-10-15
The assessment of the global performance of the state-of-the-art covariant energy density functionals and related theoretical uncertainties in the description of ground state observables has recently been performed. Based on these results, the correlations between global description of binding energies and nuclear matter properties of covariant energy density functionals have been studied in this contribution.
Wave-function inspired density functional applied to the H2/{{\\rm{H}}}_{2}^{+} challenge
NASA Astrophysics Data System (ADS)
Zhang, Igor Ying; Rinke, Patrick; Scheffler, Matthias
2016-07-01
We start from the Bethe–Goldstone equation (BGE) to derive a simple orbital-dependent correlation functional—BGE2—which terminates the BGE expansion at the second-order, but retains the self-consistent coupling of electron-pair correlations. We demonstrate that BGE2 is size consistent and one-electron ‘self-correlation’ free. The electron-pair correlation coupling ensures the correct H2 dissociation limit and gives a finite correlation energy for any system even if it has a no energy gap. BGE2 provides a good description of both H2 and {{{H}}}2+ dissociation, which is regarded as a great challenge in density functional theory (DFT). We illustrate the behavior of BGE2 analytically by considering H2 in a minimal basis. Our analysis shows that BGE2 captures essential features of the adiabatic connection path that current state-of-the-art DFT approximations do not.
Turbulent combustion analysis with various probability density functions
NASA Astrophysics Data System (ADS)
Kim, Yongmo; Chung, T. J.
A finite element method for the computation of confined, axisymmetric, turbulent diffusion flames is developed. This algorithm adopts the coupled velocity-pressure formulation to improve the covergence rate in variable-viscosity/variable-density flows. In order to minimize the numerical diffusion, the streamline upwind/Petrov-Galerkin formulation is employed. Turbulence is represented by the k-epsilon model, and the combustion process involves an irreversible one-step reaction at an infinite rate. The mean mixture properties were obtained by three methods based on the diffusion flame concept; without using a pdf, with a double-delta pdf, and with a beta pdf. A comparison is made between the combustion models with and without the pdf application, and the effect of turbulence on combustion are discussed. The numerical results are compared with available experimental data.
Core-level shifts from density-functional computations
NASA Astrophysics Data System (ADS)
Pedocchi, Luca; Russo, Nino; Salahub, Dennis R.
1993-05-01
The C 1s x-ray photoelectron spectroscopy binding energies of a series of organic (CO, CH4, C2H2, HCHO, CH3CCH, C6H6) and inorganic [Ni(CO)4, Mo(CO)6] molecules have been calculated by using the linear-combination of Gaussian-type orbitals local- and nonlocal-spin-density (LCGTO-LSD and LCGTO-NLSD) methods. The calculated C 1s chemical shifts are in very good agreement with experiment. The differences between experimental and theoretical shifts are found to be less than 0.5 eV. It is shown that the addition of nonlocal corrections improves the agreement with the experimental data.
Tabacchi, G; Hutter, J; Mundy, C
2005-04-07
A combined linear response--frozen electron density model has been implemented in a molecular dynamics scheme derived from an extended Lagrangian formalism. This approach is based on a partition of the electronic charge distribution into a frozen region described by Kim-Gordon theory, and a response contribution determined by the instaneous ionic configuration of the system. The method is free from empirical pair-potentials and the parameterization protocol involves only calculations on properly chosen subsystems. They apply this method to a series of alkali halides in different physical phases and are able to reproduce experimental structural and thermodynamic properties with an accuracy comparable to Kohn-Sham density functional calculations.
NASA Astrophysics Data System (ADS)
Balakrishnan, Nikhil; Schonfeld, Dan
2006-02-01
In this paper, we develop a new algorithm to estimate an unknown probability density function given a finite data sample using a tree shaped kernel density estimator. The algorithm formulates an integrated squared error based cost function which minimizes the quadratic divergence between the kernel density and the Parzen density estimate. The cost function reduces to a quadratic programming problem which is minimized within the maximum entropy framework. The maximum entropy principle acts as a regularizer which yields a smooth solution. A smooth density estimate enables better generalization to unseen data and offers distinct advantages in high dimensions and cases where there is limited data. We demonstrate applications of the hierarchical kernel density estimator for function interpolation and texture segmentation problems. When applied to function interpolation, the kernel density estimator improves performance considerably in situations where the posterior conditional density of the dependent variable is multimodal. The kernel density estimator allows flexible non parametric modeling of textures which improves performance in texture segmentation algorithms. We demonstrate performance on a text labeling problem which shows performance of the algorithm in high dimensions. The hierarchical nature of the density estimator enables multiresolution solutions depending on the complexity of the data. The algorithm is fast and has at most quadratic scaling in the number of kernels.
Which density functional should be used to study actinyl complexes?
Austin, Jonathan P; Burton, Neil A; Hillier, Ian H; Sundararajan, Mahesh; Vincent, Mark A
2009-02-28
The new M06 functional of Truhlar and co-workers is found to be competitive with high level ab initio methods in the study of the water exchange mechanism of the [UO(2)(OH(2))(5)](2+) ion, and of the redox potentials of the aqua complexes of [AnO(2)](2+) (An = U, Np and Pu). PMID:19209355
Evaluation of Density Functionals and Basis Sets for Carbohydrates
Technology Transfer Automated Retrieval System (TEKTRAN)
Correlated ab initio wave function calculations using MP2/aug-cc-pVTZ model chemistry have been performed for three test sets of gas phase saccharide conformations to provide reference values for their relative energies. The test sets consist of 15 conformers of alpha and beta-D-allopyranose, 15 of ...
Importance of fragmentation functions in determining polarized parton densities
NASA Astrophysics Data System (ADS)
Leader, E.; Sidorov, A. V.; Stamenov, D. B.
2014-01-01
New fragmentation functions (FFs) are extracted from a NLO QCD fit to the preliminary COMPASS data on pion and kaon multiplicities. It is shown that the new kaon FFs are very different from those of De Florian et al. (DSS) and Hirai et al. (HKNS). The sensitivity of the extracted polarized PDFs to the new FFs is discussed.
Density functional theory with spatial-symmetry breaking and configuration mixing
NASA Astrophysics Data System (ADS)
Lesinski, Thomas
2014-04-01
This article generalizes the notion of the local density of a many-body system to introduce collective coordinates as explicit degrees of freedom. It is shown that the energy of the system can be expressed as a functional of this object. The latter can in turn be factorized as the product of the square modulus of a collective wave function and a normalized collective-coordinate-dependent density. Energy minimization translates into a set of coupled equations, i.e., a local Schrödinger equation for the collective wave function and a set of Kohn-Sham equations for optimizing the normalized density at each point in the collective space. These equations reformulate the many-body problem exactly provided one is able to determine density- and collective-wave-function-dependent terms of the collective mass and potential which play a similar role to the exchange-correlation term in electronic Kohn-Sham density functional theory.
Application of the response probability density function technique to biodynamic models.
Hershey, R L; Higgins, T H
1978-01-01
A method has been developed, which we call the "response probability density function technique," which has applications in predicting the probability of injury in a wide range of biodynamic situations. The method, which was developed in connection with sonic boom damage prediction, utilized the probability density function of the excitation force and the probability density function of the sensitivity of the material being acted upon. The method is especially simple to use when both these probability density functions are lognormal. Studies thus far have shown that the stresses from sonic booms, as well as the strengths of glass and mortars, are distributed lognormally. Some biodynamic processes also have lognormal distributions and are, therefore, amenable to modeling by this technique. In particular, this paper discusses the application of the response probability density function technique to the analysis of the thoracic response to air blast and the prediction of skull fracture from head impact. PMID:623590
Carlson, Rebecca K; Li Manni, Giovanni; Sonnenberger, Andrew L; Truhlar, Donald G; Gagliardi, Laura
2015-01-13
Kohn-Sham density functional theory, resting on the representation of the electronic density and kinetic energy by a single Slater determinant, has revolutionized chemistry, but for open-shell systems, the Kohn-Sham Slater determinant has the wrong symmetry properties as compared to an accurate wave function. We have recently proposed a theory, called multiconfiguration pair-density functional theory (MC-PDFT), in which the electronic kinetic energy and classical Coulomb energy are calculated from a multiconfiguration wave function with the correct symmetry properties, and the rest of the energy is calculated from a density functional, called the on-top density functional, that depends on the density and the on-top pair density calculated from this wave function. We also proposed a simple way to approximate the on-top density functional by translation of Kohn-Sham exchange-correlation functionals. The method is much less expensive than other post-SCF methods for calculating the dynamical correlation energy starting with a multiconfiguration self-consistent-field wave function as the reference wave function, and initial tests of the theory were quite encouraging. Here, we provide a broader test of the theory by applying it to bond energies of main-group molecules and transition metal complexes, barrier heights and reaction energies for diverse chemical reactions, proton affinities, and the water dimerization energy. Averaged over 56 data points, the mean unsigned error is 3.2 kcal/mol for MC-PDFT, as compared to 6.9 kcal/mol for Kohn-Sham theory with a comparable density functional. MC-PDFT is more accurate on average than complete active space second-order perturbation theory (CASPT2) for main-group small-molecule bond energies, alkyl bond dissociation energies, transition-metal-ligand bond energies, proton affinities, and the water dimerization energy. PMID:26574206
Density functional theory for systems with mesoscopic inhomogeneities
NASA Astrophysics Data System (ADS)
Ciach, A.; Gozdz, W. T.
2016-06-01
We study the effects of fluctuations on the mesoscopic length scale on systems with mesoscopic inhomogeneities. Equations for the correlation function and for the average volume fraction are derived in the self-consistent Gaussian approximation. The equations are further simplified by postulating the expression for the structure factor consistent with scattering experiments for self-assembling systems. Predictions of the approximate theory are verified by a comparison with the exact results obtained earlier for the one-dimensional lattice model with first-neighbor attraction and third-neighbor repulsion. We find qualitative agreement for the correlation function, the equation of state and the dependence of the chemical potential μ on the volume fraction ζ. Our results confirm also that strong inhomogeneities in the disordered phase are found only in the case of strong repulsion. The inhomogeneities are reflected in an oscillatory decay of the correlation function with a very large correlation length, three inflection points in the μ ≤ft(\\zeta \\right) curve and a compressibility that for increasing ζ takes very large, very small and again very large values.
Density functional theory for systems with mesoscopic inhomogeneities.
Ciach, A; Gozdz, W T
2016-06-22
We study the effects of fluctuations on the mesoscopic length scale on systems with mesoscopic inhomogeneities. Equations for the correlation function and for the average volume fraction are derived in the self-consistent Gaussian approximation. The equations are further simplified by postulating the expression for the structure factor consistent with scattering experiments for self-assembling systems. Predictions of the approximate theory are verified by a comparison with the exact results obtained earlier for the one-dimensional lattice model with first-neighbor attraction and third-neighbor repulsion. We find qualitative agreement for the correlation function, the equation of state and the dependence of the chemical potential μ on the volume fraction ζ. Our results confirm also that strong inhomogeneities in the disordered phase are found only in the case of strong repulsion. The inhomogeneities are reflected in an oscillatory decay of the correlation function with a very large correlation length, three inflection points in the [Formula: see text] curve and a compressibility that for increasing ζ takes very large, very small and again very large values. PMID:27116121
NASA Astrophysics Data System (ADS)
Jorge, F. E.; Martins, L. S. C.; Franco, M. L.
2016-01-01
Segmented all-electron basis sets of valence double zeta quality plus polarization functions (DZP) for the elements from Ce to Lu are generated to be used with the non-relativistic and Douglas-Kroll-Hess (DKH) Hamiltonians. At the B3LYP level, the DZP-DKH atomic ionization energies and equilibrium bond lengths and atomization energies of the lanthanide trifluorides are evaluated and compared with benchmark theoretical and experimental data reported in the literature. In general, this compact size set shows to have a regular, efficient, and reliable performance. It can be particularly useful in molecular property calculations that require explicit treatment of the core electrons.
De Proft, F; Van Alsenoy, C; Peeters, A; Langenaeker, W; Geerlings, P
2002-09-01
In the Hirshfeld partitioning of the electron density, the molecular electron density is decomposed in atomic contributions, proportional to the weight of the isolated atom density in the promolecule density, constructed by superimposing the isolated atom electron densities placed on the positions the atoms have in the molecule. A maximal conservation of the information of the isolated atoms in the atoms-in-molecules is thereby secured. Atomic charges, atomic dipole moments, and Fukui functions resulting from the Hirshfeld partitioning of the electron density are computed for a large series of molecules. In a representative set of organic and hypervalent molecules, they are compared with other commonly used population analysis methods. The expected bond polarities are recovered, but the charges are much smaller compared to other methods. Condensed Fukui functions for a large number of molecules, undergoing an electrophilic or a nucleophilic attack, are computed and compared with the HOMO and LUMO densities, integrated over the Hirshfeld atoms in molecules. PMID:12116389
NASA Astrophysics Data System (ADS)
Liang, Wenkel; Isborn, Christine M.; Li, Xiaosong
2009-11-01
The calculation of doubly excited states is one of the major problems plaguing the modern day excited state workhorse methodology of linear response time dependent Hartree-Fock (TDHF) and density function theory (TDDFT). We have previously shown that the use of a resonantly tuned field within real-time TDHF and TDDFT is able to simultaneously excite both the α and β electrons to achieve the two-electron excited states of minimal basis H2 and HeH+ [C. M. Isborn and X. Li, J. Chem. Phys. 129, 204107 (2008)]. We now extend this method to many electron systems with the use of our Car-Parrinello density matrix search (CP-DMS) with a first-principles fictitious mass method for wave function optimization [X. Li, C. L. Moss, W. Liang, and Y. Feng, J. Chem. Phys. 130, 234115 (2009)]. Real-time TDHF/TDDFT is used during the application of the laser field perturbation, driving the electron density toward the doubly excited state. The CP-DMS method then converges the density to the nearest stationary state. We present these stationary state doubly excited state energies and properties at the HF and DFT levels for H2, HeH+, lithium hydride, ethylene, and butadiene.
Improving harmonic vibrational frequencies calculations in density functional theory
NASA Astrophysics Data System (ADS)
Stratmann, R. Eric; Burant, John C.; Scuseria, Gustavo E.; Frisch, Michael J.
1997-06-01
Using a previously introduced weight scheme, microbatching, and grid compression [R. E. Stratmann, G. E. Scuseria and M. J. Frisch, Chem. Phys. Lett. 257, 213 (1996)], we significantly speed up the numerical integration of the exchange-correlation contribution to the Coupled-Perturbed Kohn-Sham equations. In addition, we find that the nature of the integrand is such that it is possible to employ substantially fewer grid points in the quadrature and to use the Gaussian very Fast Multipole Method (GvFMM) with very short multipole expansions for the Coulomb contribution, with negligible loss in accuracy. As a representative example, the computational demand for the exchange-correlation portion of a coronene (C24H12) frequency calculation with a 3-21G basis is reduced by more than one order of magnitude. The overall speed up achieved in this calculation is between a factor of 4 to 6, depending on the specific functional. We also present sample calculations using polarized bases, gradient-corrected functionals, and on even larger systems (C54H18 and C96H24), to illustrate the various effects and improvements that we have accomplished.
Density-functional formalism: V xc, discontinuities, and the local density approximation
NASA Astrophysics Data System (ADS)
Gunnarsson, O.; Jones, R. O.; Schönhammer, K.
We have demonstrated that the nodal structure of the wave functions can have a great effect on the accuracy of the LSD approximation, and we have identified classes of problems where the LSD results must be treated by caution. For states with the minimum number of nodal planes consistent with the orthogonality of the orbitals, the LSD approximation usually leads to a moderate overestimate of the exchange-correlation energy. For states with additional nodal planes the exchange-correlation energy is often greatly overestimated. In atoms, the depopulation of s-orbitals can lead to large errors, and similar effects may be expected in bonding situations where sp or sd hybridization reduces the s occupancy. More work in this area is essential.
Wang, Jinlan; Zhu, Liyan; Zhang, Xiuyun; Yang, Mingli
2008-09-11
The dipole polarizabilities of Co(n)Bz(m), (n, m = 1-4, m = n, n + 1) clusters are studied by means of an all-electron gradient-corrected density functional theory and finite field method. The dipole moments are relatively large for most of the clusters, implying their asymmetric structures. The total polarizability increases rapidly as cluster size, whereas the average polarizability shows "odd-even" oscillation with relatively large values at (n, n + 1). The polarizabilities exhibit clear shape-dependent variation, and the sandwich structures have systematically larger polarizability and anisotropy than the rice-ball isomers. The dipole polarizabilities are further analyzed in terms of the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap, ionization potential, and electron delocalization volume. We conclude that the polarizability variations are determined by the interplay between the geometrical and electronic properties of the clusters. PMID:18700735
Communication: Self-interaction correction with unitary invariance in density functional theory
Pederson, Mark R.; Ruzsinszky, Adrienn; Perdew, John P.; Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122
2014-03-28
Standard spin-density functionals for the exchange-correlation energy of a many-electron ground state make serious self-interaction errors which can be corrected by the Perdew-Zunger self-interaction correction (SIC). We propose a size-extensive construction of SIC orbitals which, unlike earlier constructions, makes SIC computationally efficient, and a true spin-density functional. The SIC orbitals are constructed from a unitary transformation that is explicitly dependent on the non-interacting one-particle density matrix. When this SIC is applied to the local spin-density approximation, improvements are found for the atomization energies of molecules.
NASA Astrophysics Data System (ADS)
Zope, Rajendra R.; Dunlap, Brett I.
2006-01-01
Our recent formulation of the analytic and variational Slater-Roothaan (SR) method, which uses Gaussian basis sets to variationally express the molecular orbitals, electron density, and the one-body effective potential of density-functional theory, is reviewed. Variational fitting can be extended to the resolution of identity method, where variationality then refers to the error in each two-electron integral and not to the total energy. However, a Taylor-series analysis shows that all analytic ab initio energies calculated with variational fits to two-electron integrals are stationary. It is proposed that the appropriate fitting functions be charge neutral and that all ab initio energies be evaluated using two-center fits of the two-electron integrals. The SR method has its root in Slater's Xα method and permits an arbitrary scaling of the Slater-Gàspàr-Kohn-Sham exchange-correlation potential around each atom in the system. The scaling factors are Slater's exchange parameters α. Of several ways of choosing these parameters, two most obvious are the Hartree-Fock (HF) αHF values and the exact atomic αEA values. The former are obtained by equating the self-consistent Xα energy and the HF energies, while the latter set reproduces exact atomic energies. In this work, we examine the performance of the SR method for predicting atomization energies, bond distances, and ionization potentials using the two sets of α parameters. The atomization energies are calculated for the extended G2 set of 148 molecules for different basis-set combinations. The mean error (ME) and mean absolute error (MAE) in atomization energies are about 25 and 33kcal /mol, respectively, for the exact atomic αEA values. The HF values of exchange parameters αHF give somewhat better performance for the atomization energies with ME and MAE being about 15 and 26kcal/mol, respectively. While both sets give performance better than the local-density approximation or the HF theory, the errors in
Towards a Microscopic Reaction Description Based on Energy Density Functionals
Nobre, G A; DIetrich, F S; Escher, J E; Thompson, I J; Dupuis, M; Terasaki, J; Engel, J
2011-09-26
A microscopic calculation of reaction cross sections for nucleon-nucleus scattering has been performed by explicitly coupling the elastic channel to all particle-hole excitations in the target and one-nucleon pickup channels. The particle-hole states may be regarded as doorway states through which the flux flows to more complicated configurations, and subsequently to long-lived compound nucleus resonances. Target excitations for {sup 40,48}Ca, {sup 58}Ni, {sup 90}Zr and {sup 144}Sm were described in a random-phase framework using a Skyrme functional. Reaction cross sections obtained agree very well with experimental data and predictions of a state-of-the-art fitted optical potential. Couplings between inelastic states were found to be negligible, while the pickup channels contribute significantly. The effect of resonances from higher-order channels was assessed. Elastic angular distributions were also calculated within the same method, achieving good agreement with experimental data. For the first time observed absorptions are completely accounted for by explicit channel coupling, for incident energies between 10 and 70 MeV, with consistent angular distribution results.
A Density Functional Study of the Americium (001) Surface
NASA Astrophysics Data System (ADS)
Gao, Da; Ray, Asok Kumar
2006-03-01
Electronic structure properties of the fcc americium (001) surface, modeled by periodically repeated fcc Am (001) surface slabs, have been studied with the full-potential linearized augmented plane wave (FP-LAPW) method. The alternative basis set APW+lo is used inside the atomic spheres for chemically important orbitals that are difficult to converge, whereas LAPW is used for others. The core states are treated fully relativistically and for valence states, two levels of treatments are implemented: (1) a scalar relativistic scheme including the mass-velocity correction and the Darwin s-shift and (2) a fully relativistic scheme with spin-orbit coupling included in a second variational treatment using the scalar-relativistic eigenfunctions as basis. Our results indicate that the ground state of Am (001) surface is anti-ferromagnetic. The quantum size effects in the surface energies and the work functions of the (001) fcc americium ultra thin films (UTF) have been examined up to seven layers. In addition, the Am (001) surface properties are compared with our earlier study of the Am (111) surface.
A Hybrid Density Functional Study of Capped Silicon Carbide Nanotubes
NASA Astrophysics Data System (ADS)
Adhikari, Kapil; Ray, Asok
2011-03-01
A systematic study of fullerene hemisphere capped finite SiC nanotubes of type 1 using cluster approximation is presented. Nanotubes (3,3) and (5,0) are capped by C20 -fullerene hemisphere(C10) and (5,5) and (9,0) are capped by C60 -fullerene hemisphere (C30) . Geometries of the tubes have been spin optimized using the functional B3LYP, 3-21G* basis set and the GAUSSIAN 03 software. The study indicates that fullerene capping of a SiC nanotube changes the electronic and geometric structure properties of SiC nanotubes. For example, the binding energy per atom for infinite nanotube (5,5) is 4.993eV whereas the same nanotube with C- and Si-caps has the binding energy per atom of 5.989eV and 4.812eV, respectively. C-capped nanotubes are energetically more preferable compared to Si-capped. The HOMO-LUMO gaps of the capped nanotubes are significantly lower compared to those of infinite nanotubes. This work is supported by the Welch Foundation, Houston, Texas (Grant No. Y-1525).
Many-electron expansion: A density functional hierarchy for strongly correlated systems
NASA Astrophysics Data System (ADS)
Zhu, Tianyu; de Silva, Piotr; van Aggelen, Helen; Van Voorhis, Troy
2016-05-01
Density functional theory (DFT) is the de facto method for the electronic structure of weakly correlated systems. But for strongly correlated materials, common density functional approximations break down. Here, we derive a many-electron expansion (MEE) in DFT that accounts for successive one-, two-, three-, ... particle interactions within the system. To compute the correction terms, the density is first decomposed into a sum of localized, nodeless one-electron densities (ρi). These one-electron densities are used to construct relevant two- (ρi+ρj ), three- (ρi+ρj+ρk ), ... electron densities. Numerically exact results for these few-particle densities can then be used to correct an approximate density functional via any of several many-body expansions. We show that the resulting hierarchy gives accurate results for several important model systems: the Hubbard and Peierls-Hubbard models in 1D and the pure Hubbard model in 2D. We further show that the method is numerically convergent for strongly correlated systems: applying successively higher order corrections leads to systematic improvement of the results. MEE thus provides a hierarchy of density functional approximations that applies to both weakly and strongly correlated systems.
Bartel, J.; Bencheikh, K.; Meyer, J.
2008-02-15
For a one-body Hamiltonian obtained from the energy-density functional associated with a Skyrme effective interaction, including a tensor force, semiclassical functional densities are derived in the framework of the Extended Thomas-Fermi method, in spherical symmetry, for the kinetic energy and spin-orbit density. The structure of the self-consistent mean-field potentials constructed with such semiclassical functionals is studied. The impact of the tensor force in particular on the spin-orbit form factor clearly indicates the necessity of including such tensor-force terms in the theoretical description of atomic nuclei and their possible influence on the shell structure of exotic nuclei.
LETTER TO THE EDITOR: Mean-field dynamical density functional theory
NASA Astrophysics Data System (ADS)
Dzubiella, J.; Likos, C. N.
2003-02-01
We examine the out-of-equilibrium dynamical evolution of density profiles of ultrasoft particles under time-varying external confining potentials in three spatial dimensions. The theoretical formalism employed is the dynamical density functional theory (DDFT) of Marini, Bettolo, Marconi and Tarazona (1999 J. Chem. Phys. 110 8032), supplied by an equilibrium excess free energy functional that is essentially exact. We complement our theoretical analysis by carrying out extensive Brownian dynamics simulations. We find excellent agreement between theory and simulations for the whole time evolution of density profiles, demonstrating thereby the validity of the DDFT when an accurate equilibrium free energy functional is employed.
Dane, Markus; Gonis, Antonios
2016-07-05
Based on a computational procedure for determining the functional derivative with respect to the density of any antisymmetric N-particle wave function for a non-interacting system that leads to the density, we devise a test as to whether or not a wave function known to lead to a given density corresponds to a solution of a Schrödinger equation for some potential. We examine explicitly the case of non-interacting systems described by Slater determinants. Here, numerical examples for the cases of a one-dimensional square-well potential with infinite walls and the harmonic oscillator potential illustrate the formalism.
Excitation energies of molecules within time-independent density functional theory
Hemanadhan, M. Harbola, Manoj K.
2014-04-24
Recently proposed exchange energy functional for excited-states is tested for obtaining excitation energies of diatomic molecules. The functional is the ground-state counterpart of the local-density approximation, the modified local spin density (MLSD). The MLSD functional is tested for the N{sub 2} and CO diatomic molecules. The excitation energy obtained with the MLSD functional for the N{sub 2} molecule is in close vicinity to that obtained from the exact exchange orbital functional, Krieger, Li and Iafrate (KLI). For the CO molecule, the departure in excitation energy is observed and is due to the overcorrection of self-interaction.
Calle-Vallejo, Federico; Martínez, José Ignacio; Rossmeisl, Jan
2011-09-14
Low-temperature fuel cells are appealing alternatives to the conventional internal combustion engines for transportation applications. However, in order for them to be commercially viable, effective, stable and low-cost electrocatalysts are needed for the Oxygen Reduction Reaction (ORR) at the cathode. In this contribution, on the basis of Density Functional Theory (DFT) calculations, we show that graphitic materials with active sites composed of 4 nitrogen atoms and transition metal atoms belonging to groups 7 to 9 in the periodic table are active towards ORR, and also towards Oxygen Evolution Reaction (OER). Spin analyses suggest that the oxidation state of those elements in the active sites should in general be +2. Moreover, our results verify that the adsorption behavior of transition metals is not intrinsic, since it can be severely altered by changes in the local geometry of the active site, the chemical nature of the nearest neighbors, and the oxidation states. Nonetheless, we find that these catalysts trend-wise behave as oxides and that their catalytic activity is limited by exactly the same universal scaling relations. PMID:21796295
Debeer George, Serena; Neese, Frank
2010-02-15
Sulfur K-edge X-ray absorption spectroscopy has been proven to be a powerful tool for investigating the electronic structures of sulfur-containing coordination complexes. The full information content of the spectra can be developed through a combination of experiment and time-dependent density functional theory (TD-DFT). In this work, the necessary calibration is carried out for a range of contemporary functionals (BP86, PBE, OLYP, OPBE, B3LYP, PBE0, TPSSh) in a scalar relativistic (0(th) order regular approximation, ZORA) DFT framework. It is shown that with recently developed segmented all-electron scalar relativistic (SARC) basis sets one obtains results that are as good as with large, uncontracted basis sets. The errors in the calibrated transition energies are on the order of 0.1 eV. The error in calibrated intensities is slightly larger, but the calculations are still in excellent agreement with experiment. The behavior of full TD-DFT linear response versus the Tamm-Dancoff approximation has been evaluated with the result that two methods are almost indistinguishable. The inclusion of relativistic effects barely changes the results for first row transition metal complexes, however, the contributions become visible for second-row transition metals and reach a maximum (of an approximately 10% change in the calibration parameters) for third row transition metal species. The protocol developed here is approximately 10 times more efficient than the previously employed protocol, which was based on large, uncontracted basis sets. The calibration strategy followed here may be readily extended to other edges. PMID:20092349
Ensemble density variational methods with self- and ghost-interaction-corrected functionals
Pastorczak, Ewa; Pernal, Katarzyna
2014-05-14
Ensemble density functional theory (DFT) offers a way of predicting excited-states energies of atomic and molecular systems without referring to a density response function. Despite a significant theoretical work, practical applications of the proposed approximations have been scarce and they do not allow for a fair judgement of the potential usefulness of ensemble DFT with available functionals. In the paper, we investigate two forms of ensemble density functionals formulated within ensemble DFT framework: the Gross, Oliveira, and Kohn (GOK) functional proposed by Gross et al. [Phys. Rev. A 37, 2809 (1988)] alongside the orbital-dependent eDFT form of the functional introduced by Nagy [J. Phys. B 34, 2363 (2001)] (the acronym eDFT proposed in analogy to eHF – ensemble Hartree-Fock method). Local and semi-local ground-state density functionals are employed in both approaches. Approximate ensemble density functionals contain not only spurious self-interaction but also the so-called ghost-interaction which has no counterpart in the ground-state DFT. We propose how to correct the GOK functional for both kinds of interactions in approximations that go beyond the exact-exchange functional. Numerical applications lead to a conclusion that functionals free of the ghost-interaction by construction, i.e., eDFT, yield much more reliable results than approximate self- and ghost-interaction-corrected GOK functional. Additionally, local density functional corrected for self-interaction employed in the eDFT framework yields excitations energies of the accuracy comparable to that of the uncorrected semi-local eDFT functional.
Ensemble density variational methods with self- and ghost-interaction-corrected functionals.
Pastorczak, Ewa; Pernal, Katarzyna
2014-05-14
Ensemble density functional theory (DFT) offers a way of predicting excited-states energies of atomic and molecular systems without referring to a density response function. Despite a significant theoretical work, practical applications of the proposed approximations have been scarce and they do not allow for a fair judgement of the potential usefulness of ensemble DFT with available functionals. In the paper, we investigate two forms of ensemble density functionals formulated within ensemble DFT framework: the Gross, Oliveira, and Kohn (GOK) functional proposed by Gross et al. [Phys. Rev. A 37, 2809 (1988)] alongside the orbital-dependent eDFT form of the functional introduced by Nagy [J. Phys. B 34, 2363 (2001)] (the acronym eDFT proposed in analogy to eHF--ensemble Hartree-Fock method). Local and semi-local ground-state density functionals are employed in both approaches. Approximate ensemble density functionals contain not only spurious self-interaction but also the so-called ghost-interaction which has no counterpart in the ground-state DFT. We propose how to correct the GOK functional for both kinds of interactions in approximations that go beyond the exact-exchange functional. Numerical applications lead to a conclusion that functionals free of the ghost-interaction by construction, i.e., eDFT, yield much more reliable results than approximate self- and ghost-interaction-corrected GOK functional. Additionally, local density functional corrected for self-interaction employed in the eDFT framework yields excitations energies of the accuracy comparable to that of the uncorrected semi-local eDFT functional. PMID:24832322
Weijtens, M E; Hart, E H; Bolhuis, R L
2000-01-01
Genetically engineered expression of tumor-specific single chain antibody chimeric receptors (ch-Rec) on human T lymphocytes endow these cells with the parental monoclonal antibody (mAb) dictated tumor specificity and may be useful for clinical immuno-genetherapy. Therefore it was of importance to assess how the densities of tumor-specific receptors and tumor associated antigens (TAA), respectively, affect primary human T lymphocyte functions in relation to target cell susceptibilities to lysis. We therefore studied the functional balance between ch-Rec densities on human T lymphocytes and TAA on tumor cells. The gene construct encoding a ch-Rec derived from (1) a renal carcinoma cell (RCC) specific mouse mAb (G250), and (2) the human signal transducing Fc(epsilon)RI gamma-chain was used. To obtain ch-RecHIGH-POS and ch-RecLOW-POS T lymphocytes, two distinct retroviral vectors were used to introduce the gene constructs into primary human T lymphocytes. Levels of ch-Rec-redirected T lymphocyte mediated tumor cell lysis, as well as lymphokine production were determined using RCC lines as target/stimulator cells, which express either no or increasing densities of the TAA. A functional and dynamic balance between ch-Rec densities on cytotoxic T lymphocytes (CTLs) on the one hand and TAA densities on RCCs on the other, was found. In short, ch-RecHIGH-POS CTLs are triggered by TAAHIGH-POS as well as TAALOW-POS RCCs to lyse tumor cells and produce (IFN-gamma and TNF-alpha) lymphokine. In contrast, ch-RecLOW-POS T lymphocytes are only triggered for cytolysis and lymphokine production by relatively TAAHIGH-POS RCCs. In conclusion, (1) the activation of T lymphocyte responses is co-determined by the expression levels of the ch-Rec on T lymphocytes and the TAA on tumor cells and (2) at relatively high T lymphocyte ch-Rec expression levels the CTLs lyse tumor cells with a wide range of TAA densities. Gene Therapy (2000) 7, 35-42. PMID:10680014
NASA Technical Reports Server (NTRS)
Mcclelland, J.; Silk, J.
1979-01-01
The evolution of the two-point correlation function for the large-scale distribution of galaxies in an expanding universe is studied on the assumption that the perturbation densities lie in a Gaussian distribution centered on any given mass scale. The perturbations are evolved according to the Friedmann equation, and the correlation function for the resulting distribution of perturbations at the present epoch is calculated. It is found that: (1) the computed correlation function gives a satisfactory fit to the observed function in cosmological models with a density parameter (Omega) of approximately unity, provided that a certain free parameter is suitably adjusted; (2) the power-law slope in the nonlinear regime reflects the initial fluctuation spectrum, provided that the density profile of individual perturbations declines more rapidly than the -2.4 power of distance; and (3) both positive and negative contributions to the correlation function are predicted for cosmological models with Omega less than unity.
Introduction to Density Functional Theory: Calculations by Hand on the Helium Atom
ERIC Educational Resources Information Center
Baseden, Kyle A.; Tye, Jesse W.
2014-01-01
Density functional theory (DFT) is a type of electronic structure calculation that has rapidly gained popularity. In this article, we provide a step-by-step demonstration of a DFT calculation by hand on the helium atom using Slater's X-Alpha exchange functional on a single Gaussian-type orbital to represent the atomic wave function. This DFT…
Robust location and spread measures for nonparametric probability density function estimation.
López-Rubio, Ezequiel
2009-10-01
Robustness against outliers is a desirable property of any unsupervised learning scheme. In particular, probability density estimators benefit from incorporating this feature. A possible strategy to achieve this goal is to substitute the sample mean and the sample covariance matrix by more robust location and spread estimators. Here we use the L1-median to develop a nonparametric probability density function (PDF) estimator. We prove its most relevant properties, and we show its performance in density estimation and classification applications. PMID:19885963
Density probability distribution functions of diffuse gas in the Milky Way
NASA Astrophysics Data System (ADS)
Berkhuijsen, E. M.; Fletcher, A.
2008-10-01
In a search for the signature of turbulence in the diffuse interstellar medium (ISM) in gas density distributions, we determined the probability distribution functions (PDFs) of the average volume densities of the diffuse gas. The densities were derived from dispersion measures and HI column densities towards pulsars and stars at known distances. The PDFs of the average densities of the diffuse ionized gas (DIG) and the diffuse atomic gas are close to lognormal, especially when lines of sight at |b| < 5° and |b| >= 5° are considered separately. The PDF of
Putz, Mihai V.
2009-01-01
The density matrix theory, the ancestor of density functional theory, provides the immediate framework for Path Integral (PI) development, allowing the canonical density be extended for the many-electronic systems through the density functional closure relationship. Yet, the use of path integral formalism for electronic density prescription presents several advantages: assures the inner quantum mechanical description of the system by parameterized paths; averages the quantum fluctuations; behaves as the propagator for time-space evolution of quantum information; resembles Schrödinger equation; allows quantum statistical description of the system through partition function computing. In this framework, four levels of path integral formalism were presented: the Feynman quantum mechanical, the semiclassical, the Feynman-Kleinert effective classical, and the Fokker-Planck non-equilibrium ones. In each case the density matrix or/and the canonical density were rigorously defined and presented. The practical specializations for quantum free and harmonic motions, for statistical high and low temperature limits, the smearing justification for the Bohr’s quantum stability postulate with the paradigmatic Hydrogen atomic excursion, along the quantum chemical calculation of semiclassical electronegativity and hardness, of chemical action and Mulliken electronegativity, as well as by the Markovian generalizations of Becke-Edgecombe electronic focalization functions – all advocate for the reliability of assuming PI formalism of quantum mechanics as a versatile one, suited for analytically and/or computationally modeling of a variety of fundamental physical and chemical reactivity concepts characterizing the (density driving) many-electronic systems. PMID:20087467
Lykissa, Iliana; Li, Shu-Yi; Granqvist, Claes G.; Niklasson, Gunnar A.; Ramzan, Muhammad; Chakraborty, Sudip; Ahuja, Rajeev
2014-05-14
Thin films of V{sub 2}O{sub 5} were prepared by sputter deposition onto transparent and electrically conducting substrates and were found to be X-ray amorphous. Their electrochemical density of states was determined by chronopotentiometry and displayed a pronounced low-energy peak followed by an almost featureless contribution at higher energies. These results were compared with density functional theory calculations for amorphous V{sub 2}O{sub 5}. Significant similarities were found between measured data and computations; specifically, the experimental low-energy peak corresponds to a split-off part of the conduction band apparent in the computations. Furthermore, the calculations approximately reproduce the experimental band gap observed in optical measurements.
Chemical applications of density functional theory: F -3 anion dissociation (F -3 → F 2 + F -)
NASA Astrophysics Data System (ADS)
Sosa, Carlos; Lee, Chengteh; Fitzgerald, George; Eades, Robert A.
1993-08-01
The molecular structure and binding energies have been computed for F 2 and F -3. Local spin density (LSD) calculations were performed with the LSD Dirac exchange functional and with the Vosko, Wilk and Nusair correlation energy functional (VWN). Non-local corrections were estimated with different exchange-correlation energy functionals. The equilibrium bond lengths are within 0.01 to 0.03 Å of wave function-based ab initio results. Dissociation energies appear to be overestimated within the local density approximation. Density functional methods predict the F -3 anion to be bound by about 50.0 ± 5 kcal/mol. Vibrational frequencies were computed with VWN, LYP, BP, BLYP and PW energy functionals.
Accurate Semilocal Density Functional for Condensed-Matter Physics and Quantum Chemistry.
Tao, Jianmin; Mo, Yuxiang
2016-08-12
Most density functionals have been developed by imposing the known exact constraints on the exchange-correlation energy, or by a fit to a set of properties of selected systems, or by both. However, accurate modeling of the conventional exchange hole presents a great challenge, due to the delocalization of the hole. Making use of the property that the hole can be made localized under a general coordinate transformation, here we derive an exchange hole from the density matrix expansion, while the correlation part is obtained by imposing the low-density limit constraint. From the hole, a semilocal exchange-correlation functional is calculated. Our comprehensive test shows that this functional can achieve remarkable accuracy for diverse properties of molecules, solids, and solid surfaces, substantially improving upon the nonempirical functionals proposed in recent years. Accurate semilocal functionals based on their associated holes are physically appealing and practically useful for developing nonlocal functionals. PMID:27563956
Accurate Semilocal Density Functional for Condensed-Matter Physics and Quantum Chemistry
NASA Astrophysics Data System (ADS)
Tao, Jianmin; Mo, Yuxiang
2016-08-01
Most density functionals have been developed by imposing the known exact constraints on the exchange-correlation energy, or by a fit to a set of properties of selected systems, or by both. However, accurate modeling of the conventional exchange hole presents a great challenge, due to the delocalization of the hole. Making use of the property that the hole can be made localized under a general coordinate transformation, here we derive an exchange hole from the density matrix expansion, while the correlation part is obtained by imposing the low-density limit constraint. From the hole, a semilocal exchange-correlation functional is calculated. Our comprehensive test shows that this functional can achieve remarkable accuracy for diverse properties of molecules, solids, and solid surfaces, substantially improving upon the nonempirical functionals proposed in recent years. Accurate semilocal functionals based on their associated holes are physically appealing and practically useful for developing nonlocal functionals.
Double-hybrid density-functional theory with meta-generalized-gradient approximations
Souvi, Sidi M. O. Sharkas, Kamal; Toulouse, Julien; CNRS, UMR 7616, Laboratoire de Chimie Théorique, F-75005 Paris
2014-02-28
We extend the previously proposed one-parameter double-hybrid density-functional theory [K. Sharkas, J. Toulouse, and A. Savin, J. Chem. Phys. 134, 064113 (2011)] to meta-generalized-gradient-approximation (meta-GGA) exchange-correlation density functionals. We construct several variants of one-parameter double-hybrid approximations using the Tao-Perdew-Staroverov-Scuseria (TPSS) meta-GGA functional and test them on test sets of atomization energies and reaction barrier heights. The most accurate variant uses the uniform coordinate scaling of the density and of the kinetic energy density in the correlation functional, and improves over both standard Kohn-Sham TPSS and second-order Møller-Plesset calculations.