Theoretical studies of electronically excited states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Besley, Nicholas A.

2014-10-06

Time-dependent density functional theory is the most widely used quantum chemical method for studying molecules in electronically excited states. However, excited states can also be computed within Kohn-Sham density functional theory by exploiting methods that converge the self-consistent field equations to give excited state solutions. The usefulness of single reference self-consistent field based approaches for studying excited states is demonstrated by considering the calculation of several types of spectroscopy including the infrared spectroscopy of molecules in an electronically excited state, the rovibrational spectrum of the NO-Ar complex, core electron binding energies and the emission spectroscopy of BODIPY in water.

A space-based climatology of diurnal MLT tidal winds, temperatures and densities from UARS wind measurements

NASA Astrophysics Data System (ADS)

Svoboda, Aaron A.; Forbes, Jeffrey M.; Miyahara, Saburo

2005-11-01

A self-consistent global tidal climatology, useful for comparing and interpreting radar observations from different locations around the globe, is created from space-based Upper Atmosphere Research Satellite (UARS) horizontal wind measurements. The climatology created includes tidal structures for horizontal winds, temperature and relative density, and is constructed by fitting local (in latitude and height) UARS wind data at 95 km to a set of basis functions called Hough mode extensions (HMEs). These basis functions are numerically computed modifications to Hough modes and are globally self-consistent in wind, temperature, and density. We first demonstrate this self-consistency with a proxy data set from the Kyushu University General Circulation Model, and then use a linear weighted superposition of the HMEs obtained from monthly fits to the UARS data to extrapolate the global, multi-variable tidal structure. A brief explanation of the HMEs’ origin is provided as well as information about a public website that has been set up to make the full extrapolated data sets available.

Communication: A difference density picture for the self-consistent field ansatz.

PubMed

Parrish, Robert M; Liu, Fang; Martínez, Todd J

2016-04-07

We formulate self-consistent field (SCF) theory in terms of an interaction picture where the working variable is the difference density matrix between the true system and a corresponding superposition of atomic densities. As the difference density matrix directly represents the electronic deformations inherent in chemical bonding, this "difference self-consistent field (dSCF)" picture provides a number of significant conceptual and computational advantages. We show that this allows for a stable and efficient dSCF iterative procedure with wholly single-precision Coulomb and exchange matrix builds. We also show that the dSCF iterative procedure can be performed with aggressive screening of the pair space. These approximations are tested and found to be accurate for systems with up to 1860 atoms and >10 000 basis functions, providing for immediate overall speedups of up to 70% in the heavily optimized TeraChem SCF implementation.

Communication: A difference density picture for the self-consistent field ansatz

NASA Astrophysics Data System (ADS)

Parrish, Robert M.; Liu, Fang; Martínez, Todd J.

2016-04-01

We formulate self-consistent field (SCF) theory in terms of an interaction picture where the working variable is the difference density matrix between the true system and a corresponding superposition of atomic densities. As the difference density matrix directly represents the electronic deformations inherent in chemical bonding, this "difference self-consistent field (dSCF)" picture provides a number of significant conceptual and computational advantages. We show that this allows for a stable and efficient dSCF iterative procedure with wholly single-precision Coulomb and exchange matrix builds. We also show that the dSCF iterative procedure can be performed with aggressive screening of the pair space. These approximations are tested and found to be accurate for systems with up to 1860 atoms and >10 000 basis functions, providing for immediate overall speedups of up to 70% in the heavily optimized TeraChem SCF implementation.

Transitioning NWChem to the Next Generation of Manycore Machines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bylaska, Eric J.; Apra, E; Kowalski, Karol

The NorthWest chemistry (NWChem) modeling software is a popular molecular chemistry simulation software that was designed from the start to work on massively parallel processing supercomputers [1-3]. It contains an umbrella of modules that today includes self-consistent eld (SCF), second order Møller-Plesset perturbation theory (MP2), coupled cluster (CC), multiconguration self-consistent eld (MCSCF), selected conguration interaction (CI), tensor contraction engine (TCE) many body methods, density functional theory (DFT), time-dependent density functional theory (TDDFT), real-time time-dependent density functional theory, pseudopotential plane-wave density functional theory (PSPW), band structure (BAND), ab initio molecular dynamics (AIMD), Car-Parrinello molecular dynamics (MD), classical MD, hybrid quantum mechanicsmore » molecular mechanics (QM/MM), hybrid ab initio molecular dynamics molecular mechanics (AIMD/MM), gauge independent atomic orbital nuclear magnetic resonance (GIAO NMR), conductor like screening solvation model (COSMO), conductor-like screening solvation model based on density (COSMO-SMD), and reference interaction site model (RISM) solvation models, free energy simulations, reaction path optimization, parallel in time, among other capabilities [4]. Moreover, new capabilities continue to be added with each new release.« less

Applicability of Kerker preconditioning scheme to the self-consistent density functional theory calculations of inhomogeneous systems

NASA Astrophysics Data System (ADS)

Zhou, Yuzhi; Wang, Han; Liu, Yu; Gao, Xingyu; Song, Haifeng

2018-03-01

The Kerker preconditioner, based on the dielectric function of homogeneous electron gas, is designed to accelerate the self-consistent field (SCF) iteration in the density functional theory calculations. However, a question still remains regarding its applicability to the inhomogeneous systems. We develop a modified Kerker preconditioning scheme which captures the long-range screening behavior of inhomogeneous systems and thus improves the SCF convergence. The effectiveness and efficiency is shown by the tests on long-z slabs of metals, insulators, and metal-insulator contacts. For situations without a priori knowledge of the system, we design the a posteriori indicator to monitor if the preconditioner has suppressed charge sloshing during the iterations. Based on the a posteriori indicator, we demonstrate two schemes of the self-adaptive configuration for the SCF iteration.

Human self-control and the density of reinforcement

PubMed Central

Flora, Stephen R.; Pavlik, William B.

1992-01-01

Choice responding in adult humans on a discrete-trial button-pressing task was examined as a function of amount, delay, and overall density (points per unit time) of reinforcement. Reinforcement consisted of points that were exchangeable for money. In T 0 conditions, an impulsive response produced 4 points immediately and a self-control response produced 10 points after a delay of 15 s. In T 15 conditions, a constant delay of 15 s was added to both prereinforcer delays. Postreinforcer delays, which consisted of 15 s added to the end of each impulsive trial, equated trial durations regardless of choice, and was manipulated in both T 0 and T 15 conditions. In all conditions, choice was predicted directly from the relative reinforcement densities of the alternatives. Self-control was observed in all conditions except T 0 without postreinforcer delays, where the impulsive choices produced the higher reinforcement density. These results support previous studies showing that choice is a direct function of the relative reinforcement densities when conditioned (point) reinforcers are used. In contrast, where responding produces intrinsic (immediately consumable) reinforcers, immediacy of reinforcement appears to account for preference when density does not. PMID:16812652

Self-consistent pseudopotential calculation of the bulk properties of Mo and W

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zunger, A.; Cohen, M.L.

The bulk properties of Mo and W are calculated using the recently developed momentum-space approach for calculating total energy via a nonlocal pseudopotential. This approach avoids any shape approximation to the variational charge density (e.g., muffin tins), is fully self-consistent, and replaces the multidimensional and multicenter integrals akin to real-space representations by simple and readily convergent reciprocal-space lattice sums. We use first-principles atomic pseudopotentials which have been previously demonstrated to yield band structures and charge densities for both semiconductors and transition metals in good agreement with experiment and all-electron calculations. Using a mixed-basis representation for the crystalline wave function, wemore » are able to accurately reproduce both the localized and itinerant features of the electronic states in these systems. These first-principles pseudopotentials, together with the self-consistent density-functional representation for both the exchange and the correlation screening, yields agreement with experiment of 0.2% in the lattice parameters, 2% and 11% for the binding energies of Mo and W, respectively, and 12% and 7% for the bulk moduli of Mo and W, respectively.« less

Density-dependent covariant energy density functionals

DOE Office of Scientific and Technical Information (OSTI.GOV)

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.

Density functional theory for polymeric systems in 2D.

PubMed

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.

Extension of the self-consistent-charge density-functional tight-binding method: third-order expansion of the density functional theory total energy and introduction of a modified effective coulomb interaction.

PubMed

Yang, Yang; Yu, Haibo; York, Darrin; Cui, Qiang; Elstner, Marcus

2007-10-25

The standard self-consistent-charge density-functional-tight-binding (SCC-DFTB) method (Phys. Rev. B 1998, 58, 7260) is derived by a second-order expansion of the density functional theory total energy expression, followed by an approximation of the charge density fluctuations by charge monopoles and an effective damped Coulomb interaction between the atomic net charges. The central assumptions behind this effective charge-charge interaction are the inverse relation of atomic size and chemical hardness and the use of a fixed chemical hardness parameter independent of the atomic charge state. While these approximations seem to be unproblematic for many covalently bound systems, they are quantitatively insufficient for hydrogen-bonding interactions and (anionic) molecules with localized net charges. Here, we present an extension of the SCC-DFTB method to incorporate third-order terms in the charge density fluctuations, leading to chemical hardness parameters that are dependent on the atomic charge state and a modification of the Coulomb scaling to improve the electrostatic treatment within the second-order terms. These modifications lead to a significant improvement in the description of hydrogen-bonding interactions and proton affinities of biologically relevant molecules.

Self-consistent electrostatic potential due to trapped plasma in the magnetosphere

NASA Technical Reports Server (NTRS)

Miller, Ronald H.; Khazanov, George V.

1993-01-01

A steady state solution for the self-consistent electrostatic potential due to a plasma confined in a magnetic flux tube is considered. A steady state distribution function is constructed for the trapped particles from the constants of the motion, in the absence of waves and collisions. Using Liouville's theorem, the particle density along the geomagnetic field is determined and found to depend on the local magnetic field, self-consistent electric potential, and the equatorial plasma distribution function. A hot anisotropic magnetospheric plasma in steady state is modeled by a bi-Maxwellian at the equator. The self-consistent electric potential along the magnetic field is calculated assuming quasineutrality, and the potential drop is found to be approximately equal to the average kinetic energy of the equatorially trapped plasma. The potential is compared with that obtained by Alfven and Faelthammar (1963).

Validity of virial theorem in all-electron mixed basis density functional, Hartree–Fock, and GW calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuwahara, Riichi; Accelrys K. K., Kasumigaseki Tokyu Building 17F, 3-7-1 Kasumigaseki, Chiyoda-ku, Tokyo 100-0013; Tadokoro, Yoichi

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 inmore » 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.« less

The trust-region self-consistent field method in Kohn-Sham density-functional theory.

PubMed

Thøgersen, Lea; Olsen, Jeppe; Köhn, Andreas; Jørgensen, Poul; Sałek, Paweł; Helgaker, Trygve

2005-08-15

The trust-region self-consistent field (TRSCF) method is extended to the optimization of the Kohn-Sham energy. In the TRSCF method, both the Roothaan-Hall step and the density-subspace minimization step are replaced by trust-region optimizations of local approximations to the Kohn-Sham energy, leading to a controlled, monotonic convergence towards the optimized energy. Previously the TRSCF method has been developed for optimization of the Hartree-Fock energy, which is a simple quadratic function in the density matrix. However, since the Kohn-Sham energy is a nonquadratic function of the density matrix, the local energy functions must be generalized for use with the Kohn-Sham model. Such a generalization, which contains the Hartree-Fock model as a special case, is presented here. For comparison, a rederivation of the popular direct inversion in the iterative subspace (DIIS) algorithm is performed, demonstrating that the DIIS method may be viewed as a quasi-Newton method, explaining its fast local convergence. In the global region the convergence behavior of DIIS is less predictable. The related energy DIIS technique is also discussed and shown to be inappropriate for the optimization of the Kohn-Sham energy.

Density-functional energy gaps of solids demystified

NASA Astrophysics Data System (ADS)

Perdew, John P.; Ruzsinszky, Adrienn

2018-06-01

The fundamental energy gap of a solid is a ground-state second energy difference. Can one find the fundamental gap from the gap in the band structure of Kohn-Sham density functional theory? An argument of Williams and von Barth (WB), 1983, suggests that one can. In fact, self-consistent band-structure calculations within the local density approximation or the generalized gradient approximation (GGA) yield the fundamental gap within the same approximation for the energy. Such a calculation with the exact density functional would yield a band gap that also underestimates the fundamental gap, because the exact Kohn-Sham potential in a solid jumps up by an additive constant when one electron is added, and the WB argument does not take this effect into account. The WB argument has been extended recently to generalized Kohn-Sham theory, the simplest way to implement meta-GGAs and hybrid functionals self-consistently, with an exchange-correlation potential that is a non-multiplication operator. Since this operator is continuous, the band gap is again the fundamental gap within the same approximation, but, because the approximations are more realistic, so is the band gap. What approximations might be even more realistic?

Self-Consistent Optimization of Excited States within Density-Functional Tight-Binding.

PubMed

Kowalczyk, Tim; Le, Khoa; Irle, Stephan

2016-01-12

We present an implementation of energies and gradients for the ΔDFTB method, an analogue of Δ-self-consistent-field density functional theory (ΔSCF) within density-functional tight-binding, for the lowest singlet excited state of closed-shell molecules. Benchmarks of ΔDFTB excitation energies, optimized geometries, Stokes shifts, and vibrational frequencies reveal that ΔDFTB provides a qualitatively correct description of changes in molecular geometries and vibrational frequencies due to excited-state relaxation. The accuracy of ΔDFTB Stokes shifts is comparable to that of ΔSCF-DFT, and ΔDFTB performs similarly to ΔSCF with the PBE functional for vertical excitation energies of larger chromophores where the need for efficient excited-state methods is most urgent. We provide some justification for the use of an excited-state reference density in the DFTB expansion of the electronic energy and demonstrate that ΔDFTB preserves many of the properties of its parent ΔSCF approach. This implementation fills an important gap in the extended framework of DFTB, where access to excited states has been limited to the time-dependent linear-response approach, and affords access to rapid exploration of a valuable class of excited-state potential energy surfaces.

Self-consistent electronic structure of disordered Fe/sub 0. 65/Ni/sub 0. 35/

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, D.D.; Pinski, F.J.; Stocks, G.M.

1985-04-15

We present the results of the first ab initio calculation of the electronic structure of the disordered alloy Fe/sub 0.65/Ni/sub 0.35/. The calculation is based on the multiple-scattering coherent-potential approach (KKR-CPA) and is fully self-consistent and spin polarized. Magnetic effects are included within local-spin-density functional theory using the exchange-correlation function of Vosko--Wilk--Nusair. The most striking feature of the calculation is that electrons of different spins experience different degrees of disorder. The minority spin electrons see a very large disorder, whereas the majority spin electrons see little disorder. Consequently, the minority spin density of states is smooth compared to the verymore » structured majority spin density of states. This difference is due to a subtle balance between exchange splitting and charge neutrality.« less

Self-consistent electronic structure of disordered Fe/sub 0/ /sub 65/Ni/sub 0/ /sub 35/

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, D.D.; Pinski, F.J.; Stocks, G.M.

1984-01-01

We present the results of the first ab-initio calculation of the electronic structure of a disordered Fe/sub 0/ /sub 65/Ni/sub 0/ /sub 35/ alloy. The calculation is based on the multiple-scattering coherent-potential approach (KKR-CPA) and is fully self-consistent and spin-polarized. Magnetic effects are included within local-spin-density functional theory using the exchange-correlation function of Vosko-Wilk-Nusair. The most striking feature of the calculation is that electrons of different spins experience different degrees of disorder. The minority spin electrons see a very large disorder; whereas, the majority spin electrons see little disorder. Consequently, the minority spin density of states is smooth compared tomore » the very structured majority spin density of states. This difference is due to a subtle balance between exchange-splitting and charge neutrality. 15 references, 2 figures.« less

Gate-controlled current and inelastic electron tunneling spectrum of benzene: a self-consistent study.

PubMed

Liang, Y Y; Chen, H; Mizuseki, H; Kawazoe, Y

2011-04-14

We use density functional theory based nonequilibrium Green's function to self-consistently study the current through the 1,4-benzenedithiol (BDT). The elastic and inelastic tunneling properties through this Au-BDT-Au molecular junction are simulated, respectively. For the elastic tunneling case, it is found that the current through the tilted molecule can be modulated effectively by the external gate field, which is perpendicular to the phenyl ring. The gate voltage amplification comes from the modulation of the interaction between the electrodes and the molecules in the junctions. For the inelastic case, the electron tunneling scattered by the molecular vibrational modes is considered within the self-consistent Born approximation scheme, and the inelastic electron tunneling spectrum is calculated.

The ordering of symmetric diblock copolymers: A comparison of self-consistent-field and density functional approaches

NASA Astrophysics Data System (ADS)

Nath, Shyamal K.; McCoy, John D.; Curro, John G.; Saunders, Randall S.

1997-02-01

Polymer reference interaction site model (PRISM) based density functional (DF) theory is used to evaluate the structure and thermodynamics of structurally symmetric, freely jointed, diblock chains with 0.50 volume fraction. These results are compared to the results of self-consistent-field (SCF) theory. Agreement between the predictions of the SCF and DF theories is found for the lamella spacing well above the order-disorder transition (ODT) and for the qualitative behavior of the interfacial thickness as a function of both chain length and Flory-Huggins χ parameter. Disagreement is found for the magnitude of the interfacial thickness where DF theory indicates that the thickness is 1.7±0.2 times larger than that predicted by SCF theory. It appears that behavior on the monomer length scale is sensitive to system specific details which are neglected by SCF theory.

Periodic Pulay method for robust and efficient convergence acceleration of self-consistent field iterations

DOE PAGES

Banerjee, Amartya S.; Suryanarayana, Phanish; Pask, John E.

2016-01-21

Pulay's Direct Inversion in the Iterative Subspace (DIIS) method is one of the most widely used mixing schemes for accelerating the self-consistent solution of electronic structure problems. In this work, we propose a simple generalization of DIIS in which Pulay extrapolation is performed at periodic intervals rather than on every self-consistent field iteration, and linear mixing is performed on all other iterations. Lastly, we demonstrate through numerical tests on a wide variety of materials systems in the framework of density functional theory that the proposed generalization of Pulay's method significantly improves its robustness and efficiency.

Orbital-free bond breaking via machine learning

NASA Astrophysics Data System (ADS)

Snyder, John C.; Rupp, Matthias; Hansen, Katja; Blooston, Leo; Müller, Klaus-Robert; Burke, Kieron

2013-12-01

Using a one-dimensional model, we explore the ability of machine learning to approximate the non-interacting kinetic energy density functional of diatomics. This nonlinear interpolation between Kohn-Sham reference calculations can (i) accurately dissociate a diatomic, (ii) be systematically improved with increased reference data and (iii) generate accurate self-consistent densities via a projection method that avoids directions with no data. With relatively few densities, the error due to the interpolation is smaller than typical errors in standard exchange-correlation functionals.

Density Functional Calculations for the Neutron Star Matter at Subnormal Density

NASA Astrophysics Data System (ADS)

Kashiwaba, Yu; Nakatsukasa, Takashi

The pasta phases of nuclear matter, whose existence is suggested at low density, may influence observable properties of neutron stars. In order to investigate properties of the neutron star matter, we calculate self-consistent solutions for the ground states of slab-like phase using the microscopic density functional theory with Bloch wave functions. The calculations are performed at each point of fixed average density and proton fraction (\\bar{ρ },Yp), varying the lattice constant of the unit cell. For small Yp values, the dripped neutrons emerge in the ground state, while the protons constitute the slab (crystallized) structure. The shell effect of protons affects the thickness of the slab nuclei.

A Sparse Self-Consistent Field Algorithm and Its Parallel Implementation: Application to Density-Functional-Based Tight Binding.

PubMed

Scemama, Anthony; Renon, Nicolas; Rapacioli, Mathias

2014-06-10

We present an algorithm and its parallel implementation for solving a self-consistent problem as encountered in Hartree-Fock or density functional theory. The algorithm takes advantage of the sparsity of matrices through the use of local molecular orbitals. The implementation allows one to exploit efficiently modern symmetric multiprocessing (SMP) computer architectures. As a first application, the algorithm is used within the density-functional-based tight binding method, for which most of the computational time is spent in the linear algebra routines (diagonalization of the Fock/Kohn-Sham matrix). We show that with this algorithm (i) single point calculations on very large systems (millions of atoms) can be performed on large SMP machines, (ii) calculations involving intermediate size systems (1000-100 000 atoms) are also strongly accelerated and can run efficiently on standard servers, and (iii) the error on the total energy due to the use of a cutoff in the molecular orbital coefficients can be controlled such that it remains smaller than the SCF convergence criterion.

Active Space Dependence in Multiconfiguration Pair-Density Functional Theory.

PubMed

Sharma, Prachi; Truhlar, Donald G; Gagliardi, Laura

2018-02-13

In multiconfiguration pair-density functional theory (MC-PDFT), multiconfiguration self-consistent-field calculations and on-top density functionals are combined to describe both static and dynamic correlation. Here, we investigate how the MC-PDFT total energy and its components depend on the active space choice in the case of the H 2 and N 2 molecules. The active space dependence of the on-top pair density, the total density, the ratio of on-top pair density to half the square of the electron density, and the satisfaction of the virial theorem are also explored. We find that the density and on-top pair density do not change significantly with changes in the active space. However, the on-top ratio does change significantly with respect to active space change, and this affects the on-top energy. This study provides a foundation for designing on-top density functionals and automatizing the active space choice in MC-PDFT.

Integrated fusion simulation with self-consistent core-pedestal coupling

DOE PAGES

Meneghini, O.; Snyder, P. B.; Smith, S. P.; ...

2016-04-20

In this study, accurate prediction of fusion performance in present and future tokamaks requires taking into account the strong interplay between core transport, pedestal structure, current profile and plasma equilibrium. An integrated modeling workflow capable of calculating the steady-state self- consistent solution to this strongly-coupled problem has been developed. The workflow leverages state-of-the-art components for collisional and turbulent core transport, equilibrium and pedestal stability. Validation against DIII-D discharges shows that the workflow is capable of robustly pre- dicting the kinetic profiles (electron and ion temperature and electron density) from the axis to the separatrix in good agreement with the experiments.more » An example application is presented, showing self-consistent optimization for the fusion performance of the 15 MA D-T ITER baseline scenario as functions of the pedestal density and ion effective charge Z eff.« less

Self-contained filtered density function

DOE PAGES

Nouri, Arash G.; Nik, Mehdi B.; Givi, Pope; ...

2017-09-18

The filtered density function (FDF) closure is extended to a “self-contained” format to include the subgrid-scale (SGS) statistics of all of the hydro-thermo-chemical variables in turbulent flows. These are the thermodynamic pressure, the specific internal energy, the velocity vector, and the composition field. In this format, the model is comprehensive and facilitates large-eddy simulation (LES) of flows at both low and high compressibility levels. A transport equation is developed for the joint pressure-energy-velocity-composition filtered mass density function (PEVC-FMDF). In this equation, the effect of convection appears in closed form. The coupling of the hydrodynamics and thermochemistry is modeled via amore » set of stochastic differential equation for each of the transport variables. This yields a self-contained SGS closure. We demonstrated how LES is conducted of a turbulent shear flow with transport of a passive scalar. Finally, the consistency of the PEVC-FMDF formulation is established, and its overall predictive capability is appraised via comparison with direct numerical simulation (DNS) data.« less

Self-contained filtered density function

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nouri, Arash G.; Nik, Mehdi B.; Givi, Pope

The filtered density function (FDF) closure is extended to a “self-contained” format to include the subgrid-scale (SGS) statistics of all of the hydro-thermo-chemical variables in turbulent flows. These are the thermodynamic pressure, the specific internal energy, the velocity vector, and the composition field. In this format, the model is comprehensive and facilitates large-eddy simulation (LES) of flows at both low and high compressibility levels. A transport equation is developed for the joint pressure-energy-velocity-composition filtered mass density function (PEVC-FMDF). In this equation, the effect of convection appears in closed form. The coupling of the hydrodynamics and thermochemistry is modeled via amore » set of stochastic differential equation for each of the transport variables. This yields a self-contained SGS closure. We demonstrated how LES is conducted of a turbulent shear flow with transport of a passive scalar. Finally, the consistency of the PEVC-FMDF formulation is established, and its overall predictive capability is appraised via comparison with direct numerical simulation (DNS) data.« less

Self-contained filtered density function

NASA Astrophysics Data System (ADS)

Nouri, A. G.; Nik, M. B.; Givi, P.; Livescu, D.; Pope, S. B.

2017-09-01

The filtered density function (FDF) closure is extended to a "self-contained" format to include the subgrid-scale (SGS) statistics of all of the hydro-thermo-chemical variables in turbulent flows. These are the thermodynamic pressure, the specific internal energy, the velocity vector, and the composition field. In this format, the model is comprehensive and facilitates large-eddy simulation (LES) of flows at both low and high compressibility levels. A transport equation is developed for the joint pressure-energy-velocity-composition filtered mass density function (PEVC-FMDF). In this equation, the effect of convection appears in closed form. The coupling of the hydrodynamics and thermochemistry is modeled via a set of stochastic differential equation for each of the transport variables. This yields a self-contained SGS closure. For demonstration, LES is conducted of a turbulent shear flow with transport of a passive scalar. The consistency of the PEVC-FMDF formulation is established, and its overall predictive capability is appraised via comparison with direct numerical simulation (DNS) data.

Full self-consistency in the Fermi-orbital self-interaction correction

NASA Astrophysics Data System (ADS)

Yang, Zeng-hui; Pederson, Mark R.; Perdew, John P.

2017-05-01

The Perdew-Zunger self-interaction correction cures many common problems associated with semilocal density functionals, but suffers from a size-extensivity problem when Kohn-Sham orbitals are used in the correction. Fermi-Löwdin-orbital self-interaction correction (FLOSIC) solves the size-extensivity problem, allowing its use in periodic systems and resulting in better accuracy in finite systems. Although the previously published FLOSIC algorithm Pederson et al., J. Chem. Phys. 140, 121103 (2014)., 10.1063/1.4869581 appears to work well in many cases, it is not fully self-consistent. This would be particularly problematic for systems where the occupied manifold is strongly changed by the correction. In this paper, we demonstrate a different algorithm for FLOSIC to achieve full self-consistency with only marginal increase of computational cost. The resulting total energies are found to be lower than previously reported non-self-consistent results.

Dielectric function and plasmons in graphene: A self-consistent-field calculation within a Markovian master equation formalism

DOE PAGES

Karimi, F.; Davoody, A. H.; Knezevic, I.

2016-05-12

We introduce a method for calculating the dielectric function of nanostructures with an arbitrary band dispersion and Bloch wave functions. The linear response of a dissipative electronic system to an external electromagnetic field is calculated by a self-consistent-field approach within a Markovian master equation formalism (SCF-MMEF) coupled with full-wave electromagnetic equations. The SCF-MMEF accurately accounts for several concurrent scattering mechanisms. The method captures interband electron-hole-pair generation, as well as the interband and intraband electron scattering with phonons and impurities. We employ the SCF-MMEF to calculate the dielectric function, complex conductivity, and loss function for supported graphene. From the loss-function maximum,more » we obtain plasmon dispersion and propagation length for different substrate types [nonpolar diamondlike carbon (DLC) and polar SiO 2 and hBN], impurity densities, carrier densities, and temperatures. Plasmons on the two polar substrates are suppressed below the highest surface phonon energy, while the spectrum is broad on the nonpolar DLC. Plasmon propagation lengths are comparable on polar and nonpolar substrates and are on the order of tens of nanometers, considerably shorter than previously reported. As a result, they improve with fewer impurities, at lower temperatures, and at higher carrier densities.« less

Collision dynamics of H+ + N2 at low energies based on time-dependent density-functional theory

NASA Astrophysics Data System (ADS)

Yu, W.; Zhang, Y.; Zhang, F. S.; Hutton, R.; Zou, Y.; Gao, C.-Z.; Wei, B.

2018-02-01

Using time-dependent density-functional theory at the level of local density approximation augmented by a self-interaction correction and coupled non-adiabatically to molecular dynamics, we study, from a theoretical perspective, scattering dynamics of the proton in collisions with the N2 molecule at 30 eV. Nine different collision configurations are employed to analyze the proton energy loss spectra, electron depletion, scattering angles and self-interaction effects. Our results agree qualitatively with the experimental data and previous theoretical calculations. The discrepancies are ascribed to the limitation of the theoretical models in use. We find that self-interaction effects can significantly influence the electron capture and the excited diatomic vibrational motion, which is in consistent with other calculations. In addition, it is found that the molecular structure can be readily retrieved from the proton energy loss spectra due to a significant momentum transfer in head-on collisions.

Self-Consistent Determination of Atomic Charges of Ionic Liquid through a Combination of Molecular Dynamics Simulation and Density Functional Theory.

PubMed

Ishizuka, Ryosuke; Matubayasi, Nobuyuki

2016-02-09

A self-consistent scheme is developed to determine the atomic partial charges of ionic liquid. Molecular dynamics (MD) simulation was conducted to sample a set of ion configurations, and these configurations were subject to density functional theory (DFT) calculations to determine the partial charges. The charges were then averaged and used as inputs for the subsequent MD simulation, and MD and DFT calculations were repeated until the MD results are not altered any more. We applied this scheme to 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl) imide ([C1mim][NTf2]) and investigated its structure and dynamics as a function of temperature. At convergence, the average ionic charges were ±0.84 e at 350 K due to charge transfer among ions, where e is the elementary charge, while the reduced ionic charges do not affect strongly the density of [C1mim][NTf2] and radial distribution function. Instead, major effects are found on the energetics and dynamics, with improvements of the overestimated heat of vaporization and the too slow motions of ions observed in MD simulations using commonly used force fields.

Excited State Studies of Polyacenes Using the All-Order Constricted Variational Density Functional Theory with Orbital Relaxation.

PubMed

Senn, Florian; Krykunov, Mykhaylo

2015-10-22

For the polyacenes series from naphthalene to hexacene, we present the vertical singlet excitation energies 1 (1)La and 1 (1)Lb, as well as the first triplet excitation energies obtained by the all-order constricted variational density functional theory with orbital relaxation (R-CV(∞)-DFT). R-CV(∞)-DFT is a further development of variational density functional theory (CV(∞)-DFT), which has already been successfully applied for the calculation of the vertical singlet excitation energies (1)La and (1)Lb for polyacenes,15 and we show that one obtains consistent excitation energies using the local density approximation as a functional for singlet as well as for triplet excitations when going beyond the linear response theory. Furthermore, we apply self-consistent field density functional theory (ΔSCF-DFT) and compare the obtained excitation energies for the first triplet excitations T1, where, due to the character of the transition, ΔSCF-DFT and R-CV(∞)-DFT become numerically equivalent, and for the singlet excitations 1 (1)La and 1 (1)Lb, where the two methods differ.

Structural, vibrational, and quasiparticle properties of the Peierls semiconductor BaBiO3 : A hybrid functional and self-consistent GW+vertex-corrections study

NASA Astrophysics Data System (ADS)

Franchini, C.; Sanna, A.; Marsman, M.; Kresse, G.

2010-02-01

BaBiO3 is characterized by a charge disproportionation with half of the Bi atoms possessing a valence 3+ and half a valence 5+ . Because of self-interaction errors, local- and semilocal-density functionals fail to describe the charge disproportionation quantitatively, yielding a too small structural distortion and no band gap. Using hybrid functionals, we obtain a satisfactory description of the structural, electronic, optical, and vibrational properties of BaBiO3 . The results obtained using GW (Green’s function G and screened Coulomb potential W) based schemes on top of hybrid functionals, including fully self-consistent GW calculations with vertex corrections in the dielectric screening, qualitatively confirm the Heyd-Scuseria-Ernzerhof picture but a systematic overestimation of the band gap by about 0.4 eV is observed.

Hartree-Fock theory of the inhomogeneous electron gas at a jellium metal surface: Rigorous upper bounds to the surface energy and accurate work functions

NASA Astrophysics Data System (ADS)

Sahni, V.; Ma, C. Q.

1980-12-01

The inhomogeneous electron gas at a jellium metal surface is studied in the Hartree-Fock approximation by Kohn-Sham density functional theory. Rigorous upper bounds to the surface energy are derived by application of the Rayleigh-Ritz variational principle for the energy, the surface kinetic, electrostatic, and nonlocal exchange energy functionals being determined exactly for the accurate linear-potential model electronic wave functions. The densities obtained by the energy minimization constraint are then employed to determine work-function results via the variationally accurate "displaced-profile change-in-self-consistent-field" expression. The theoretical basis of this non-self-consistent procedure and its demonstrated accuracy for the fully correlated system (as treated within the local-density approximation for exchange and correlation) leads us to conclude these results for the surface energies and work functions to be essentially exact. Work-function values are also determined by the Koopmans'-theorem expression, both for these densities as well as for those obtained by satisfaction of the constraint set on the electrostatic potential by the Budd-Vannimenus theorem. The use of the Hartree-Fock results in the accurate estimation of correlation-effect contributions to these surface properties of the nonuniform electron gas is also indicated. In addition, the original work and approximations made by Bardeen in this attempt at a solution of the Hartree-Fock problem are briefly reviewed in order to contrast with the present work.

Isoscalar and isovector giant resonances in a self-consistent phonon coupling approach

NASA Astrophysics Data System (ADS)

Lyutorovich, N.; Tselyaev, V.; Speth, J.; Krewald, S.; Grümmer, F.; Reinhard, P.-G.

2015-10-01

We present fully self-consistent calculations of isoscalar giant monopole and quadrupole as well as isovector giant dipole resonances in heavy and light nuclei. The description is based on Skyrme energy-density functionals determining the static Hartree-Fock ground state and the excitation spectra within random-phase approximation (RPA) and RPA extended by including the quasiparticle-phonon coupling at the level of the time-blocking approximation (TBA). All matrix elements were derived consistently from the given energy-density functional and calculated without any approximation. As a new feature in these calculations, the single-particle continuum was included thus avoiding the artificial discretization usually implied in RPA and TBA. The step to include phonon coupling in TBA leads to small, but systematic, down shifts of the centroid energies of the giant resonances. These shifts are similar in size for all Skyrme parametrizations investigated here. After all, we demonstrate that one can find Skyrme parametrizations which deliver a good simultaneous reproduction of all three giant resonances within TBA.

Self-consistent Green's function embedding for advanced electronic structure methods based on a dynamical mean-field concept

NASA Astrophysics Data System (ADS)

Chibani, Wael; Ren, Xinguo; Scheffler, Matthias; Rinke, Patrick

2016-04-01

We present an embedding scheme for periodic systems that facilitates the treatment of the physically important part (here a unit cell or a supercell) with advanced electronic structure methods, that are computationally too expensive for periodic systems. The rest of the periodic system is treated with computationally less demanding approaches, e.g., Kohn-Sham density-functional theory, in a self-consistent manner. Our scheme is based on the concept of dynamical mean-field theory formulated in terms of Green's functions. Our real-space dynamical mean-field embedding scheme features two nested Dyson equations, one for the embedded cluster and another for the periodic surrounding. The total energy is computed from the resulting Green's functions. The performance of our scheme is demonstrated by treating the embedded region with hybrid functionals and many-body perturbation theory in the GW approach for simple bulk systems. The total energy and the density of states converge rapidly with respect to the computational parameters and approach their bulk limit with increasing cluster (i.e., computational supercell) size.

Testing variations of the GW approximation on strongly correlated transition metal oxides: hematite (α-Fe2O3) as a benchmark.

PubMed

Liao, Peilin; Carter, Emily A

2011-09-07

Quantitative characterization of low-lying excited electronic states in materials is critical for the development of solar energy conversion materials. The many-body Green's function method known as the GW approximation (GWA) directly probes states corresponding to photoemission and inverse photoemission experiments, thereby determining the associated band structure. Several versions of the GW approximation with different levels of self-consistency exist in the field. While the GWA based on density functional theory (DFT) works well for conventional semiconductors, less is known about its reliability for strongly correlated semiconducting materials. Here we present a systematic study of the GWA using hematite (α-Fe(2)O(3)) as the benchmark material. We analyze its performance in terms of the calculated photoemission/inverse photoemission band gaps, densities of states, and dielectric functions. Overall, a non-self-consistent G(0)W(0) using input from DFT+U theory produces physical observables in best agreement with experiments. This journal is © the Owner Societies 2011

Binding and Diffusion of Lithium in Graphite: Quantum Monte Carlo Benchmarks and Validation of van der Waals Density Functional Methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ganesh, P.; Kim, Jeongnim; Park, Changwon

2014-11-03

In highly accurate diffusion quantum Monte Carlo (QMC) studies of the adsorption and diffusion of atomic lithium in AA-stacked graphite are compared with van der Waals-including density functional theory (DFT) calculations. Predicted QMC lattice constants for pure AA graphite agree with experiment. Pure AA-stacked graphite is shown to challenge many van der Waals methods even when they are accurate for conventional AB graphite. Moreover, the highest overall DFT accuracy, considering pure AA-stacked graphite as well as lithium binding and diffusion, is obtained by the self-consistent van der Waals functional vdW-DF2, although errors in binding energies remain. Empirical approaches based onmore » point charges such as DFT-D are inaccurate unless the local charge transfer is assessed. Our results demonstrate that the lithium carbon system requires a simultaneous highly accurate description of both charge transfer and van der Waals interactions, favoring self-consistent approaches.« less

Performance of extended Lagrangian schemes for molecular dynamics simulations with classical polarizable force fields and density functional theory

NASA Astrophysics Data System (ADS)

Vitale, Valerio; Dziedzic, Jacek; Albaugh, Alex; Niklasson, Anders M. N.; Head-Gordon, Teresa; Skylaris, Chris-Kriton

2017-03-01

Iterative energy minimization with the aim of achieving self-consistency is a common feature of Born-Oppenheimer molecular dynamics (BOMD) and classical molecular dynamics with polarizable force fields. In the former, the electronic degrees of freedom are optimized, while the latter often involves an iterative determination of induced point dipoles. The computational effort of the self-consistency procedure can be reduced by re-using converged solutions from previous time steps. However, this must be done carefully, as not to break time-reversal symmetry, which negatively impacts energy conservation. Self-consistent schemes based on the extended Lagrangian formalism, where the initial guesses for the optimized quantities are treated as auxiliary degrees of freedom, constitute one elegant solution. We report on the performance of two integration schemes with the same underlying extended Lagrangian structure, which we both employ in two radically distinct regimes—in classical molecular dynamics simulations with the AMOEBA polarizable force field and in BOMD simulations with the Onetep linear-scaling density functional theory (LS-DFT) approach. Both integration schemes are found to offer significant improvements over the standard (unpropagated) molecular dynamics formulation in both the classical and LS-DFT regimes.

Performance of extended Lagrangian schemes for molecular dynamics simulations with classical polarizable force fields and density functional theory.

PubMed

Vitale, Valerio; Dziedzic, Jacek; Albaugh, Alex; Niklasson, Anders M N; Head-Gordon, Teresa; Skylaris, Chris-Kriton

2017-03-28

Iterative energy minimization with the aim of achieving self-consistency is a common feature of Born-Oppenheimer molecular dynamics (BOMD) and classical molecular dynamics with polarizable force fields. In the former, the electronic degrees of freedom are optimized, while the latter often involves an iterative determination of induced point dipoles. The computational effort of the self-consistency procedure can be reduced by re-using converged solutions from previous time steps. However, this must be done carefully, as not to break time-reversal symmetry, which negatively impacts energy conservation. Self-consistent schemes based on the extended Lagrangian formalism, where the initial guesses for the optimized quantities are treated as auxiliary degrees of freedom, constitute one elegant solution. We report on the performance of two integration schemes with the same underlying extended Lagrangian structure, which we both employ in two radically distinct regimes-in classical molecular dynamics simulations with the AMOEBA polarizable force field and in BOMD simulations with the Onetep linear-scaling density functional theory (LS-DFT) approach. Both integration schemes are found to offer significant improvements over the standard (unpropagated) molecular dynamics formulation in both the classical and LS-DFT regimes.

Performance of extended Lagrangian schemes for molecular dynamics simulations with classical polarizable force fields and density functional theory

DOE PAGES

Vitale, Valerio; Dziedzic, Jacek; Albaugh, Alex; ...

2017-03-28

Iterative energy minimization with the aim of achieving self-consistency is a common feature of Born-Oppenheimer molecular dynamics (BOMD) and classical molecular dynamics with polarizable force fields. In the former, the electronic degrees of freedom are optimized, while the latter often involves an iterative determination of induced point dipoles. The computational effort of the self-consistency procedure can be reduced by re-using converged solutions from previous time steps. However, this must be done carefully, as not to break time-reversal symmetry, which negatively impacts energy conservation. Self-consistent schemes based on the extended Lagrangian formalism, where the initial guesses for the optimized quantities aremore » treated as auxiliary degrees of freedom, constitute one elegant solution. We report on the performance of two integration schemes with the same underlying extended Lagrangian structure, which we both employ in two radically distinct regimes—in classical molecular dynamics simulations with the AMOEBA polarizable force field and in BOMD simulations with the Onetep linear-scaling density functional theory (LS-DFT) approach. Furthermore, both integration schemes are found to offer significant improvements over the standard (unpropagated) molecular dynamics formulation in both the classical and LS-DFT regimes.« less

Performance of extended Lagrangian schemes for molecular dynamics simulations with classical polarizable force fields and density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vitale, Valerio; Dziedzic, Jacek; Albaugh, Alex

Iterative energy minimization with the aim of achieving self-consistency is a common feature of Born-Oppenheimer molecular dynamics (BOMD) and classical molecular dynamics with polarizable force fields. In the former, the electronic degrees of freedom are optimized, while the latter often involves an iterative determination of induced point dipoles. The computational effort of the self-consistency procedure can be reduced by re-using converged solutions from previous time steps. However, this must be done carefully, as not to break time-reversal symmetry, which negatively impacts energy conservation. Self-consistent schemes based on the extended Lagrangian formalism, where the initial guesses for the optimized quantities aremore » treated as auxiliary degrees of freedom, constitute one elegant solution. We report on the performance of two integration schemes with the same underlying extended Lagrangian structure, which we both employ in two radically distinct regimes—in classical molecular dynamics simulations with the AMOEBA polarizable force field and in BOMD simulations with the Onetep linear-scaling density functional theory (LS-DFT) approach. Furthermore, both integration schemes are found to offer significant improvements over the standard (unpropagated) molecular dynamics formulation in both the classical and LS-DFT regimes.« less

First-principles studies of electronic, transport and bulk properties of pyrite FeS2

NASA Astrophysics Data System (ADS)

Banjara, Dipendra; Mbolle, Augustine; Malozovsky, Yuriy; Franklin, Lashounda; Bagayoko, Diola

We present results of ab-initio, self-consistent density functional theory (DFT) calculations of electronic, transport, and bulk properties of pyrite FeS2. We employed a local density approximation (LDA) potential and the linear combination of atomic orbitals (LCAO) formalism, following the Bagayoko, Zhao and Williams (BZW) method, as enhanced by Ekuma and Franklin (BZW-EF). The BZW-EF method requires successive, self consistent calculations with increasing basis sets to reach the ground state of the system under study. We report the band structure, the band gap, total and partial densities of states, effective masses, and the bulk modulus. Work funded in part by the US Department of Energy (DOE), National Nuclear Security Administration (NNSA) (Award No.DE-NA0002630), the National Science Foundation (NSF) (Award No, 1503226), LaSPACE, and LONI-SUBR.

Orbital-Dependent Density Functionals for Chemical Catalysis

DTIC Science & Technology

2011-02-16

E2 and SN2 Reactions: Effects of the Choice of Density Functional, Basis Set, and Self-Consistent Iterations," Y. Zhao and D. G. Truhlar, Journal...for  the  anti-­‐ E2,  syn-­‐E2,  and   SN2  pathways  of  the  reactions  of  F-­‐  and  Cl-­‐  with  CH3CH2F  and

Justifying quasiparticle self-consistent schemes via gradient optimization in Baym-Kadanoff theory.

PubMed

Ismail-Beigi, Sohrab

2017-09-27

The question of which non-interacting Green's function 'best' describes an interacting many-body electronic system is both of fundamental interest as well as of practical importance in describing electronic properties of materials in a realistic manner. Here, we study this question within the framework of Baym-Kadanoff theory, an approach where one locates the stationary point of a total energy functional of the one-particle Green's function in order to find the total ground-state energy as well as all one-particle properties such as the density matrix, chemical potential, or the quasiparticle energy spectrum and quasiparticle wave functions. For the case of the Klein functional, our basic finding is that minimizing the length of the gradient of the total energy functional over non-interacting Green's functions yields a set of self-consistent equations for quasiparticles that is identical to those of the quasiparticle self-consistent GW (QSGW) (van Schilfgaarde et al 2006 Phys. Rev. Lett. 96 226402-4) approach, thereby providing an a priori justification for such an approach to electronic structure calculations. In fact, this result is general, applies to any self-energy operator, and is not restricted to any particular approximation, e.g., the GW approximation for the self-energy. The approach also shows that, when working in the basis of quasiparticle states, solving the diagonal part of the self-consistent Dyson equation is of primary importance while the off-diagonals are of secondary importance, a common observation in the electronic structure literature of self-energy calculations. Finally, numerical tests and analytical arguments show that when the Dyson equation produces multiple quasiparticle solutions corresponding to a single non-interacting state, minimizing the length of the gradient translates into choosing the solution with largest quasiparticle weight.

Ground-state energies and highest occupied eigenvalues of atoms in exchange-only density-functional theory

NASA Astrophysics Data System (ADS)

Li, Yan; Harbola, Manoj K.; Krieger, J. B.; Sahni, Viraht

1989-11-01

The exchange-correlation potential of the Kohn-Sham density-functional theory has recently been interpreted as the work required to move an electron against the electric field of its Fermi-Coulomb hole charge distribution. In this paper we present self-consistent results for ground-state total energies and highest occupied eigenvalues of closed subshell atoms as obtained by this formalism in the exchange-only approximation. The total energies, which are an upper bound, lie within 50 ppm of Hartree-Fock theory for atoms heavier than Be. The highest occupied eigenvalues, as a consequence of this interpretation, approximate well the experimental ionization potentials. In addition, the self-consistently calculated exchange potentials are very close to those of Talman and co-workers [J. D. Talman and W. F. Shadwick, Phys. Rev. A 14, 36 (1976); K. Aashamar, T. M. Luke, and J. D. Talman, At. Data Nucl. Data Tables 22, 443 (1978)].

Self-consistent self-interaction corrected density functional theory calculations for atoms using Fermi-Löwdin orbitals: Optimized Fermi-orbital descriptors for Li-Kr

NASA Astrophysics Data System (ADS)

Kao, Der-you; Withanage, Kushantha; Hahn, Torsten; Batool, Javaria; Kortus, Jens; Jackson, Koblar

2017-10-01

In the Fermi-Löwdin orbital method for implementing self-interaction corrections (FLO-SIC) in density functional theory (DFT), the local orbitals used to make the corrections are generated in a unitary-invariant scheme via the choice of the Fermi orbital descriptors (FODs). These are M positions in 3-d space (for an M-electron system) that can be loosely thought of as classical electron positions. The orbitals that minimize the DFT energy including the SIC are obtained by finding optimal positions for the FODs. In this paper, we present optimized FODs for the atoms from Li-Kr obtained using an unbiased search method and self-consistent FLO-SIC calculations. The FOD arrangements display a clear shell structure that reflects the principal quantum numbers of the orbitals. We describe trends in the FOD arrangements as a function of atomic number. FLO-SIC total energies for the atoms are presented and are shown to be in close agreement with the results of previous SIC calculations that imposed explicit constraints to determine the optimal local orbitals, suggesting that FLO-SIC yields the same solutions for atoms as these computationally demanding earlier methods, without invoking the constraints.

How important is self-consistency for the dDsC density dependent dispersion correction?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brémond, Éric; Corminboeuf, Clémence, E-mail: clemence.corminboeuf@epfl.ch; Golubev, Nikolay

2014-05-14

The treatment of dispersion interactions is ubiquitous but computationally demanding for seamless ab initio approaches. A highly popular and simple remedy consists in correcting for the missing interactions a posteriori by adding an attractive energy term summed over all atom pairs to standard density functional approximations. These corrections were originally based on atom pairwise parameters and, hence, had a strong touch of empiricism. To overcome such limitations, we recently proposed a robust system-dependent dispersion correction, dDsC, that is computed from the electron density and that provides a balanced description of both weak inter- and intramolecular interactions. From the theoretical pointmore » of view and for the sake of increasing reliability, we here verify if the self-consistent implementation of dDsC impacts ground-state properties such as interaction energies, electron density, dipole moments, geometries, and harmonic frequencies. In addition, we investigate the suitability of the a posteriori scheme for molecular dynamics simulations, for which the analysis of the energy conservation constitutes a challenging tests. Our study demonstrates that the post-SCF approach in an excellent approximation.« less

Dynamic Structure Factor: An Introduction

NASA Astrophysics Data System (ADS)

Sturm, K.

1993-02-01

The doubly differential cross-section for weak inelastic scattering of waves or particles by manybody systems is derived in Born approximation and expressed in terms of the dynamic structure factor according to van Hove. The application of this very general scheme to scattering of neutrons, x-rays and high-energy electrons is discussed briefly. The dynamic structure factor, which is the space and time Fourier transform of the density-density correlation function, is a property of the many-body system independent of the external probe and carries information on the excitation spectrum of the system. The relation of the electronic structure factor to the density-density response function defined in linear-response theory is shown using the fluctuation-dissipation theorem. This is important for calculations, since the response function can be calculated approximately from the independent-particle response function in self-consistent field approximations, such as the random-phase approximation or the local-density approximation of the density functional theory. Since the density-density response function also determines the dielectric function, the dynamic structure can be expressed by the dielectric function.

Transport characteristics of a ZnMgO/ZnO hetero junction and the effect of temperature and Mg content

NASA Astrophysics Data System (ADS)

Uslu, Salih; Yarar, Zeki

2017-02-01

The Ensemble Monte Carlo method is used to calculate the transport characteristics of two dimensional electron gas (2DEG) at a ZnMgO/ZnO hetero structure. The spontaneous and piezoelectric polarizations are considered and there is no intentional doping in either material. Numerical Schrödinger and Poisson equations are solved self consistently to obtain the scattering rates of various scattering mechanisms. The density of carriers, each energy sub bands, potential profile and corresponding wave functions are obtained from the self consistent calculations. The self consistent sub band wave functions of acoustic and optic phonon scattering and interface roughness scattering are used in Monte Carlo method to obtain transport characteristics at ZnMgO/ZnO junction. Two dimensional electron gas confined to ZnMgO/ZnO hetero structure is studied and the effect of temperature and Mg content are investigated.

Effect of Spin-Orbit Coupling on the Actinide Dioxides AnO2 (An=Th, Pa, U, Np, Pu, and Am): A Screened Hybrid Density Functional Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wen, Xiaodong; Martin, Richard L.; Roy, Lindsay E.

2012-10-21

We present a systematic comparison of the lattice structures, electronic density of states, and band gaps of actinide dioxides, AnO₂ (An=Th, Pa, U, Np, Pu, and Am) predicted by the Heyd-Scuseria-Ernzerhof screened hybrid density functional (HSE) with the self-consistent inclusion of spin-orbit coupling(SOC). The computed HSE lattice constants and band gaps of AnO₂ are in consistently good agreement with the available experimental data across the series, and differ little from earlier HSE results without SOC. ThO₂ is a simple band insulator (f⁰), while PaO₂, UO₂, and NpO₂ are predicted to be Mott insulators. The remainders (PuO₂ and AmO₂) show considerablemore » O2p/An5f mixing and are classified as charge-transfer insulators. We also compare our results for UO₂, NpO₂, and PuO₂with the PBE+U, self interaction correction (SIC), and dynamic mean-field theory (DMFT) many-body approximations.« less

Dust particle radial confinement in a dc glow discharge.

PubMed

Sukhinin, G I; Fedoseev, A V; Antipov, S N; Petrov, O F; Fortov, V E

2013-01-01

A self-consistent nonlocal model of the positive column of a dc glow discharge with dust particles is presented. Radial distributions of plasma parameters and the dust component in an axially homogeneous glow discharge are considered. The model is based on the solution of a nonlocal Boltzmann equation for the electron energy distribution function, drift-diffusion equations for ions, and the Poisson equation for a self-consistent electric field. The radial distribution of dust particle density in a dust cloud was fixed as a given steplike function or was chosen according to an equilibrium Boltzmann distribution. The balance of electron and ion production in argon ionization by an electron impact and their losses on the dust particle surface and on the discharge tube walls is taken into account. The interrelation of discharge plasma and the dust cloud is studied in a self-consistent way, and the radial distributions of the discharge plasma and dust particle parameters are obtained. It is shown that the influence of the dust cloud on the discharge plasma has a nonlocal behavior, e.g., density and charge distributions in the dust cloud substantially depend on the plasma parameters outside the dust cloud. As a result of a self-consistent evolution of plasma parameters to equilibrium steady-state conditions, ionization and recombination rates become equal to each other, electron and ion radial fluxes become equal to zero, and the radial component of electric field is expelled from the dust cloud.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parrish, Robert M.; Liu, Fang; Martínez, Todd J., E-mail: toddjmartinez@gmail.com

We formulate self-consistent field (SCF) theory in terms of an interaction picture where the working variable is the difference density matrix between the true system and a corresponding superposition of atomic densities. As the difference density matrix directly represents the electronic deformations inherent in chemical bonding, this “difference self-consistent field (dSCF)” picture provides a number of significant conceptual and computational advantages. We show that this allows for a stable and efficient dSCF iterative procedure with wholly single-precision Coulomb and exchange matrix builds. We also show that the dSCF iterative procedure can be performed with aggressive screening of the pair space.more » These approximations are tested and found to be accurate for systems with up to 1860 atoms and >10 000 basis functions, providing for immediate overall speedups of up to 70% in the heavily optimized TERACHEM SCF implementation.« less

Structural, electronic and vibrational properties of lanthanide monophosphide at high pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Panchal, J. M., E-mail: amitjignesh@yahoo.co.in; Department of Physics, University School of Sciences, Gujarat University, Ahmedabad 380009, Gujarat; Joshi, Mitesh

2016-05-06

A first-principles plane wave self-consistent method with the ultra-soft-pseudopotential scheme in the framework of the density functional theory (DFT) is performed to study structural, electronic and vibrational properties of LaP for Rock-salt (NaCl/Bl) and Cesium-chloride (CsCl/B2) phases. The instability of Rock-salt (NaCl/Bl) phases around the transition is discussed. Conclusions based on electronic energy band structure, density of state, phonon dispersion and phonon density of states in both phases are outlined. The calculated results are consistence and confirm the successful applicability of quasi-harmonic phonon theory for structural instability studies for the alloys.

Many-body Green’s function theory for electron-phonon interactions: The Kadanoff-Baym approach to spectral properties of the Holstein dimer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Säkkinen, Niko; Peng, Yang; Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin-Dahlem

2015-12-21

We present a Kadanoff-Baym formalism to study time-dependent phenomena for systems of interacting electrons and phonons in the framework of many-body perturbation theory. The formalism takes correctly into account effects of the initial preparation of an equilibrium state and allows for an explicit time-dependence of both the electronic and phononic degrees of freedom. The method is applied to investigate the charge neutral and non-neutral excitation spectra of a homogeneous, two-site, two-electron Holstein model. This is an extension of a previous study of the ground state properties in the Hartree (H), partially self-consistent Born (Gd) and fully self-consistent Born (GD) approximationsmore » published in Säkkinen et al. [J. Chem. Phys. 143, 234101 (2015)]. Here, the homogeneous ground state solution is shown to become unstable for a sufficiently strong interaction while a symmetry-broken ground state solution is shown to be stable in the Hartree approximation. Signatures of this instability are observed for the partially self-consistent Born approximation but are not found for the fully self-consistent Born approximation. By understanding the stability properties, we are able to study the linear response regime by calculating the density-density response function by time-propagation. This amounts to a solution of the Bethe-Salpeter equation with a sophisticated kernel. The results indicate that none of the approximations is able to describe the response function during or beyond the bipolaronic crossover for the parameters investigated. Overall, we provide an extensive discussion on when the approximations are valid and how they fail to describe the studied exact properties of the chosen model system.« less

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

DOE PAGES

Tao, Jianmin; Ye, Lin -Hui; Duan, Yuhua

2017-11-20

The primary goal of Kohn–Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao–Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree–Fock density yields the exchange and correlation energies in good agreement with the Optimizedmore » Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Lastly, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.« less

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

NASA Astrophysics Data System (ADS)

Tao, Jianmin; Ye, Lin-Hui; Duan, Yuhua

2017-12-01

The primary goal of Kohn-Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao-Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew-Burke-Ernzerhof (PBE), Tao-Perdew-Staroverov-Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree-Fock density yields the exchange and correlation energies in good agreement with the Optimized Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Finally, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, Jianmin; Ye, Lin -Hui; Duan, Yuhua

The primary goal of Kohn–Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao–Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree–Fock density yields the exchange and correlation energies in good agreement with the Optimizedmore » Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Lastly, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.« less

The van Hove distribution function for Brownian hard spheres: Dynamical test particle theory and computer simulations for bulk dynamics

NASA Astrophysics Data System (ADS)

Hopkins, Paul; Fortini, Andrea; Archer, Andrew J.; Schmidt, Matthias

2010-12-01

We describe a test particle approach based on dynamical density functional theory (DDFT) for studying the correlated time evolution of the particles that constitute a fluid. Our theory provides a means of calculating the van Hove distribution function by treating its self and distinct parts as the two components of a binary fluid mixture, with the "self " component having only one particle, the "distinct" component consisting of all the other particles, and using DDFT to calculate the time evolution of the density profiles for the two components. We apply this approach to a bulk fluid of Brownian hard spheres and compare to results for the van Hove function and the intermediate scattering function from Brownian dynamics computer simulations. We find good agreement at low and intermediate densities using the very simple Ramakrishnan-Yussouff [Phys. Rev. B 19, 2775 (1979)] approximation for the excess free energy functional. Since the DDFT is based on the equilibrium Helmholtz free energy functional, we can probe a free energy landscape that underlies the dynamics. Within the mean-field approximation we find that as the particle density increases, this landscape develops a minimum, while an exact treatment of a model confined situation shows that for an ergodic fluid this landscape should be monotonic. We discuss possible implications for slow, glassy, and arrested dynamics at high densities.

When combined X-ray and polarized neutron diffraction data challenge high-level calculations: spin-resolved electron density of an organic radical.

PubMed

Voufack, Ariste Bolivard; Claiser, Nicolas; Lecomte, Claude; Pillet, Sébastien; Pontillon, Yves; Gillon, Béatrice; Yan, Zeyin; Gillet, Jean Michel; Marazzi, Marco; Genoni, Alessandro; Souhassou, Mohamed

2017-08-01

Joint refinement of X-ray and polarized neutron diffraction data has been carried out in order to determine charge and spin density distributions simultaneously in the nitronyl nitroxide (NN) free radical Nit(SMe)Ph. For comparison purposes, density functional theory (DFT) and complete active-space self-consistent field (CASSCF) theoretical calculations were also performed. Experimentally derived charge and spin densities show significant differences between the two NO groups of the NN function that are not observed from DFT theoretical calculations. On the contrary, CASSCF calculations exhibit the same fine details as observed in spin-resolved joint refinement and a clear asymmetry between the two NO groups.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saperstein, E. E., E-mail: saper@mbslab.kiae.ru; Tolokonnikov, S. V.

Recent results obtained on the basis of the self-consistent theory of finite Fermi systems by employing the energy density functional proposed by Fayans and his coauthors are surveyed. These results are compared with the predictions of Skyrme–Hartree–Fock theory involving several popular versions of the Skyrme energy density functional. Spherical nuclei are predominantly considered. The charge radii of even and odd nuclei and features of low-lying 2{sup +} excitations in semimagic nuclei are discussed briefly. The single-particle energies ofmagic nuclei are examined inmore detail with allowance for corrections to mean-field theory that are induced by particle coupling to low-lying collective surfacemore » excitations (phonons). The importance of taking into account, in this problem, nonpole (tadpole) diagrams, which are usually disregarded, is emphasized. The spectroscopic factors of magic and semimagic nuclei are also considered. In this problem, only the surface term stemming from the energy dependence induced in the mass operator by the exchange of surface phonons is usually taken into account. The volume contribution associated with the energy dependence initially present in the mass operator within the self-consistent theory of finite Fermi systems because of the exchange of high-lying particle–hole excitations is also included in the spectroscopic factor. The results of the first studies that employed the Fayans energy density functional for deformed nuclei are also presented.« less

Conduction in fully ionized liquid metals

NASA Technical Reports Server (NTRS)

Stevenson, D. J.; Ashcroft, N. W.

1973-01-01

Electron transport is considered in high density fully ionized liquid metals. Ionic structure is described in terms of hard-sphere correlation functions and the scattering is determined from self-consistently screened point ions. Applications to the physical properties of the deep interior of Jupiter are briefly considered.

Calculated electronic, transport, and related properties of zinc blende boron arsenide (zb-BAs)

NASA Astrophysics Data System (ADS)

Nwigboji, Ifeanyi H.; Malozovsky, Yuriy; Franklin, Lashounda; Bagayoko, Diola

2016-10-01

We present the results from ab-initio, self-consistent density functional theory (DFT) calculations of electronic, transport, and bulk properties of zinc blende boron arsenide. We utilized the local density approximation potential of Ceperley and Alder, as parameterized by Vosko and his group, the linear combination of Gaussian orbitals formalism, and the Bagayoko, Zhao, and Williams (BZW) method, as enhanced by Ekuma and Franklin (BZW-EF), in carrying out our completely self-consistent calculations. With this method, the results of our calculations have the full, physical content of density functional theory (DFT). Our results include electronic energy bands, densities of states, effective masses, and the bulk modulus. Our calculated, indirect band gap of 1.48 eV, from Γ to a conduction band minimum close to X, for the room temperature lattice constant of 4.777 Å, is in an excellent agreement with the experimental value of 1.46 ± 0.02 eV. We thoroughly explain the reasons for the excellent agreement between our findings and corresponding, experimental ones. This work provides a confirmation of the capability of DFT to describe accurately properties of materials, if the computations adhere strictly to the conditions of validity of DFT, as done by the BZW-EF method.

Multi-charge-state molecular dynamics and self-diffusion coefficient in the warm dense matter regime

NASA Astrophysics Data System (ADS)

Fu, Yongsheng; Hou, Yong; Kang, Dongdong; Gao, Cheng; Jin, Fengtao; Yuan, Jianmin

2018-01-01

We present a multi-ion molecular dynamics (MIMD) simulation and apply it to calculating the self-diffusion coefficients of ions with different charge-states in the warm dense matter (WDM) regime. First, the method is used for the self-consistent calculation of electron structures of different charge-state ions in the ion sphere, with the ion-sphere radii being determined by the plasma density and the ion charges. The ionic fraction is then obtained by solving the Saha equation, taking account of interactions among different charge-state ions in the system, and ion-ion pair potentials are computed using the modified Gordon-Kim method in the framework of temperature-dependent density functional theory on the basis of the electron structures. Finally, MIMD is used to calculate ionic self-diffusion coefficients from the velocity correlation function according to the Green-Kubo relation. A comparison with the results of the average-atom model shows that different statistical processes will influence the ionic diffusion coefficient in the WDM regime.

Density-functional expansion methods: Grand challenges.

PubMed

Giese, Timothy J; York, Darrin M

2012-03-01

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.

Self-consistent generalized Langevin-equation theory for liquids of nonspherically interacting particles.

PubMed

Elizondo-Aguilera, L F; Zubieta Rico, P F; Ruiz-Estrada, H; Alarcón-Waess, O

2014-11-01

A self-consistent generalized Langevin-equation theory is proposed to describe the self- and collective dynamics of a liquid of linear Brownian particles. The equations of motion for the spherical harmonics projections of the collective and self-intermediate-scattering functions, F_{lm,lm}(k,t) and F_{lm,lm}^{S}(k,t), are derived as a contraction of the description involving the stochastic equations of the corresponding tensorial one-particle density n_{lm}(k,t) and the translational (α=T) and rotational (α=R) current densities j_{lm}^{α}(k,t). Similar to the spherical case, these dynamic equations require as an external input the equilibrium structural properties of the system contained in the projections of the static structure factor, denoted by S_{lm,lm}(k). Complementing these exact equations with simple (Vineyard-like) approximate relations for the collective and the self-memory functions we propose a closed self-consistent set of equations for the dynamic properties involved. In the long-time asymptotic limit, these equations become the so-called bifurcation equations, whose solutions (the nonergodicity parameters) can be written, extending the spherical case, in terms of one translational and one orientational scalar dynamic order parameter, γ_{T} and γ_{R}, which characterize the possible dynamical arrest transitions of the system. As a concrete illustrative application of this theory we determine the dynamic arrest diagram of the dipolar hard-sphere fluid. In qualitative agreement with mode coupling theory, the present self-consistent equations also predict three different regions in the state space spanned by the macroscopic control parameters η (volume fraction) and T* (scaled temperature): a region of fully ergodic states, a region of mixed states, in which the translational degrees of freedom become arrested while the orientational degrees of freedom remain ergodic, and a region of fully nonergodic states.

Second-order perturbation theory with a density matrix renormalization group self-consistent field reference function: theory and application to the study of chromium dimer.

PubMed

Kurashige, Yuki; Yanai, Takeshi

2011-09-07

We present a second-order perturbation theory based on a density matrix renormalization group self-consistent field (DMRG-SCF) reference function. The method reproduces the solution of the complete active space with second-order perturbation theory (CASPT2) when the DMRG reference function is represented by a sufficiently large number of renormalized many-body basis, thereby being named DMRG-CASPT2 method. The DMRG-SCF is able to describe non-dynamical correlation with large active space that is insurmountable to the conventional CASSCF method, while the second-order perturbation theory provides an efficient description of dynamical correlation effects. The capability of our implementation is demonstrated for an application to the potential energy curve of the chromium dimer, which is one of the most demanding multireference systems that require best electronic structure treatment for non-dynamical and dynamical correlation as well as large basis sets. The DMRG-CASPT2/cc-pwCV5Z calculations were performed with a large (3d double-shell) active space consisting of 28 orbitals. Our approach using large-size DMRG reference addressed the problems of why the dissociation energy is largely overestimated by CASPT2 with the small active space consisting of 12 orbitals (3d4s), and also is oversensitive to the choice of the zeroth-order Hamiltonian. © 2011 American Institute of Physics

Density-functional expansion methods: evaluation of LDA, GGA, and meta-GGA functionals and different integral approximations.

PubMed

Giese, Timothy J; York, Darrin M

2010-12-28

We extend the Kohn-Sham potential energy expansion (VE) to include variations of the kinetic energy density and use the VE formulation with a 6-31G* basis to perform a "Jacob's ladder" comparison of small molecule properties using density functionals classified as being either LDA, GGA, or meta-GGA. We show that the VE reproduces standard Kohn-Sham DFT results well if all integrals are performed without further approximation, and there is no substantial improvement in using meta-GGA functionals relative to GGA functionals. The advantages of using GGA versus LDA functionals becomes apparent when modeling hydrogen bonds. We furthermore examine the effect of using integral approximations to compute the zeroth-order energy and first-order matrix elements, and the results suggest that the origin of the short-range repulsive potential within self-consistent charge density-functional tight-binding methods mainly arises from the approximations made to the first-order matrix elements.

Transitioning NWChem to the Next Generation of Manycore Machines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bylaska, Eric J.; Apra, Edoardo; Kowalski, Karol

The NorthWest Chemistry (NWChem) modeling software is a popular molecular chemistry simulation software that was designed from the start to work on massively parallel processing supercomputers[6, 28, 49]. It contains an umbrella of modules that today includes Self Consistent Field (SCF), second order Mller-Plesset perturbation theory (MP2), Coupled Cluster, multi-conguration selfconsistent eld (MCSCF), selected conguration interaction (CI), tensor contraction engine (TCE) many body methods, density functional theory (DFT), time-dependent density functional theory (TDDFT), real time time-dependent density functional theory, pseudopotential plane-wave density functional theory (PSPW), band structure (BAND), ab initio molecular dynamics, Car-Parrinello molecular dynamics, classical molecular dynamics (MD), QM/MM,more » AIMD/MM, GIAO NMR, COSMO, COSMO-SMD, and RISM solvation models, free energy simulations, reaction path optimization, parallel in time, among other capabilities[ 22]. Moreover new capabilities continue to be added with each new release.« less

Modeling of electron cyclotron resonance discharges

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meyyappan, M.; Govindan, T.R.

The current trend in plasma processing is the development of high density plasma sources to achieve high deposition and etch rates, uniformity over large ares, and low wafer damage. Here, is a simple model to predict the spatially-averaged plasma characteristics of electron cyclotron resonance (ECR) reactors is presented. The model consists of global conservation equations for species concentration, electron density and energy. A gas energy balance is used to predict the neutral temperature self-consistently. The model is demonstrated for an ECR argon discharge. The predicted behavior of the discharge as a function of system variables agrees well with experimental observations.

Self-consistent predictor/corrector algorithms for stable and efficient integration of the time-dependent Kohn-Sham equation

NASA Astrophysics Data System (ADS)

Zhu, Ying; Herbert, John M.

2018-01-01

The "real time" formulation of time-dependent density functional theory (TDDFT) involves integration of the time-dependent Kohn-Sham (TDKS) equation in order to describe the time evolution of the electron density following a perturbation. This approach, which is complementary to the more traditional linear-response formulation of TDDFT, is more efficient for computation of broad-band spectra (including core-excited states) and for systems where the density of states is large. Integration of the TDKS equation is complicated by the time-dependent nature of the effective Hamiltonian, and we introduce several predictor/corrector algorithms to propagate the density matrix, one of which can be viewed as a self-consistent extension of the widely used modified-midpoint algorithm. The predictor/corrector algorithms facilitate larger time steps and are shown to be more efficient despite requiring more than one Fock build per time step, and furthermore can be used to detect a divergent simulation on-the-fly, which can then be halted or else the time step modified.

Real-Space Multiple-Scattering Theory and Its Applications at Exascale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eisenbach, Markus; Wang, Yang

In recent decades, the ab initio methods based on density functional theory (DFT) (Hohenberg and Kohn 1964, Kohn and Sham 1965) have become a widely used tool in computational materials science, which allows theoretical prediction of physical properties of materials from the first principles and theoretical interpretation of new physical phenomena found in experiments. In the framework of DFT, the original problem that requires solving a quantum mechanical equation for a many-electron system is reduced to a one-electron problem that involves an electron moving in an effective field, while the effective field potential is made up of an electrostatic potential,more » also known as Hartree potential, arising from the electronic and ion charge distribution in space and an exchange–correlation potential, which is a function of the electron density and encapsulates the exchange and correlation effects of the many-electron system. Even though the exact functional form of the exchange-correlation potential is formally unknown, a local density approximation (LDA) or a generalized gradient approximation (GGA) is usually applied so that the calculation of the exchange–correlation potential, as well as the exchange–correlation energy, becomes tractable while a required accuracy is retained. Based on DFT, ab initio electronic structure calculations for a material generally involve a self-consistent process that iterates between two computational tasks: (1) solving an one-electron Schrödinger equation, also known as Kohn–Sham equation, to obtain the electron density and, if needed, the magnetic moment density, and (2) solving the Poisson equation to obtain the electrostatic potential corresponding to the electron density and constructing the effective potential by adding the exchange–correlation potential to the electrostatic potential. This self-consistent process proceeds until a convergence criteria is reached.« less

A DYNAMIC DENSITY FUNCTIONAL THEORY APPROACH TO DIFFUSION IN WHITE DWARFS AND NEUTRON STAR ENVELOPES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Diaw, A.; Murillo, M. S.

2016-09-20

We develop a multicomponent hydrodynamic model based on moments of the Born–Bogolyubov–Green–Kirkwood–Yvon hierarchy equations for physical conditions relevant to astrophysical plasmas. These equations incorporate strong correlations through a density functional theory closure, while transport enters through a relaxation approximation. This approach enables the introduction of Coulomb coupling correction terms into the standard Burgers equations. The diffusive currents for these strongly coupled plasmas is self-consistently derived. The settling of impurities and its impact on cooling can be greatly affected by strong Coulomb coupling, which we show can be quantified using the direct correlation function.

Intersubband Transitions in InAs/AlSb Quantum Wells

NASA Technical Reports Server (NTRS)

Li, J.; Koloklov, K.; Ning, C. Z.; Larraber, D. C.; Khodaparast, G. A.; Kono, J.; Ueda, K.; Nakajima, Y.; Sasa, S.; Inoue, M.

2003-01-01

We have studied intersubband transitions in InAs/AlSb quantum wells experimentally and theoretically. Experimentally, we performed polarization-resolved infrared absorption spectroscopy to measure intersubband absorption peak frequencies and linewidths as functions of temperature (from 4 K to room temperature) and quantum well width (from a few nm to 10 nm). To understand experimental results, we performed a self-consistent 8-band k-p band-structure calculation including spatial charge separation. Based on the calculated band structure, we developed a set of density matrix equations to compute TE and TM optical transitions self-consistently, including both interband and intersubband channels. This density matrix formalism is also ideal for the inclusion of various many-body effects, which are known to be important for intersubband transitions. Detailed comparison between experimental data and theoretical simulations is presented.

Self-consistent Hartree-Fock RPA calculations in 208Pb

NASA Astrophysics Data System (ADS)

Taqi, Ali H.; Ali, Mohammed S.

2018-01-01

The nuclear structure of 208Pb is studied in the framework of the self-consistent random phase approximation (SCRPA). The Hartree-Fock mean field and single particle states are used to implement a completely SCRPA with Skyrme-type interactions. The Hamiltonian is diagonalised within a model space using five Skyrme parameter sets, namely LNS, SkI3, SkO, SkP and SLy4. In view of the huge number of the existing Skyrme-force parameterizations, the question remains which of them provide the best description of data. The approach attempts to accurately describe the structure of the spherical even-even nucleus 208Pb. To illustrate our approach, we compared the binding energy, charge density distribution, excitation energy levels scheme with the available experimental data. Moreover, we calculated isoscalar and isovector monopole, dipole, and quadrupole transition densities and strength functions.

Surface symmetry energy of nuclear energy density functionals

NASA Astrophysics Data System (ADS)

Nikolov, N.; Schunck, N.; Nazarewicz, W.; Bender, M.; Pei, J.

2011-03-01

We study the bulk deformation properties of the Skyrme nuclear energy density functionals (EDFs). 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 EDFs. 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.

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.

Rationale for switching to nonlocal functionals in density functional theory.

PubMed

Lazić, P; Atodiresei, N; Caciuc, V; Brako, R; Gumhalter, B; Blügel, S

2012-10-24

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.

Extension of the Kohn-Sham formulation of density functional theory to finite temperature

NASA Astrophysics Data System (ADS)

Gonis, A.; Däne, M.

2018-05-01

Based on Mermin's extension of the Hohenberg and Kohn theorems to non-zero temperature, the Kohn-Sham formulation of density functional theory (KS-DFT) is generalized to finite temperature. We show that present formulations are inconsistent with Mermin's functional containing expressions, in particular describing the Coulomb energy, that defy derivation and are even in violation of rules of logical inference. More; current methodology is in violation of fundamental laws of both quantum and classical mechanics. Based on this feature, we demonstrate the impossibility of extending the KS formalism to finite temperature through the self-consistent solutions of the single-particle Schrödinger equation of T > 0. Guided by the form of Mermin's functional that depends on the eigenstates of a Hamiltonian, determined at T = 0, we base our extension of KS-DFT on the determination of the excited states of a non-interacting system at the zero of temperature. The resulting formulation is consistent with that of Mermin constructing the free energy at T > 0 in terms of the excited states of a non-interacting Hamiltonian (system) that, within the KS formalism, are described by Slater determinants. To determine the excited states at T = 0 use is made of the extension of the Hohenberg and Kohn theorems to excited states presented in previous work applied here to a non-interacting collection of replicas of a non-interacting N-particle system, whose ground state density is taken to match that of K non-interacting replicas of an interacting N-particle system at T = 0 . The formalism allows for an ever denser population of the excitation spectrum of a Hamiltonian, within the KS approximation. The form of the auxiliary potential, (Kohn-Sham potential), is formally identical to that in the ground state formalism with the contribution of the Coulomb energy provided by the derivative of the Coulomb energy in all excited states taken into account. Once the excited states are determined, the minimum of the free energy within the KS formalism follows immediately in the form of Mermin's functional, but with the exact excited states in that functional represented by Slater determinants obtained through self-consistency conditions at the zero of temperature. It is emphasized that, in departure from all existing formulations, no self-consistency conditions are implemented at finite T; as we show, in fact, such formulations are rigorously blocked.

Site-occupation embedding theory using Bethe ansatz local density approximations

NASA Astrophysics Data System (ADS)

Senjean, Bruno; Nakatani, Naoki; Tsuchiizu, Masahisa; Fromager, Emmanuel

2018-06-01

Site-occupation embedding theory (SOET) is an alternative formulation of density functional theory (DFT) for model Hamiltonians where the fully interacting Hubbard problem is mapped, in principle exactly, onto an impurity-interacting (rather than a noninteracting) one. It provides a rigorous framework for combining wave-function (or Green function)-based methods with DFT. In this work, exact expressions for the per-site energy and double occupation of the uniform Hubbard model are derived in the context of SOET. As readily seen from these derivations, the so-called bath contribution to the per-site correlation energy is, in addition to the latter, the key density functional quantity to model in SOET. Various approximations based on Bethe ansatz and perturbative solutions to the Hubbard and single-impurity Anderson models are constructed and tested on a one-dimensional ring. The self-consistent calculation of the embedded impurity wave function has been performed with the density-matrix renormalization group method. It has been shown that promising results are obtained in specific regimes of correlation and density. Possible further developments have been proposed in order to provide reliable embedding functionals and potentials.

Objective Molecular Dynamics with Self-consistent Charge Density Functional Tight-Binding (SCC-DFTB) Method

NASA Astrophysics Data System (ADS)

Dumitrica, Traian; Hourahine, Ben; Aradi, Balint; Frauenheim, Thomas

We discus the coupling of the objective boundary conditions into the SCC density functional-based tight binding code DFTB+. The implementation is enabled by a generalization to the helical case of the classical Ewald method, specifically by Ewald-like formulas that do not rely on a unit cell with translational symmetry. The robustness of the method in addressing complex hetero-nuclear nano- and bio-fibrous systems is demonstrated with illustrative simulations on a helical boron nitride nanotube, a screw dislocated zinc oxide nanowire, and an ideal double-strand DNA. Work supported by NSF CMMI 1332228.

Phosphorene quantum dot-fullerene nanocomposites for solar energy conversion: An unexplored inorganic-organic nanohybrid with novel photovoltaic properties

NASA Astrophysics Data System (ADS)

Rajbanshi, Biplab; Kar, Moumita; Sarkar, Pallavi; Sarkar, Pranab

2017-10-01

Using the self-consistent charge density-functional based tight-binding (SCC-DFTB) method, coupled with time-dependent density functional theory (TDDFT) calculations, for the first time we explore the possibility of use of phosphorene quantum dots in solar energy harvesting devices. The phosphorene quantum dots-fullerene (PQDs-PCBA) nanocomposites show type-II band alignment indicating spatial separation of charge carriers. The TDDFT calculations also show that the PQD-fullerene nanocomposites seem to be exciting material for future generation solar energy harvester, with extremely fast charge transfer and very poor recombination rate.

Self-consistent average-atom scheme for electronic structure of hot and dense plasmas of mixture.

PubMed

Yuan, Jianmin

2002-10-01

An average-atom model is proposed to treat the electronic structures of hot and dense plasmas of mixture. It is assumed that the electron density consists of two parts. The first one is a uniform distribution with a constant value, which is equal to the electron density at the boundaries between the atoms. The second one is the total electron density minus the first constant distribution. The volume of each kind of atom is proportional to the sum of the charges of the second electron part and of the nucleus within each atomic sphere. By this way, one can make sure that electrical neutrality is satisfied within each atomic sphere. Because the integration of the electron charge within each atom needs the size of that atom in advance, the calculation is carried out in a usual self-consistent way. The occupation numbers of electron on the orbitals of each kind of atom are determined by the Fermi-Dirac distribution with the same chemical potential for all kinds of atoms. The wave functions and the orbital energies are calculated with the Dirac-Slater equations. As examples, the electronic structures of the mixture of Au and Cd, water (H2O), and CO2 at a few temperatures and densities are presented.

Calculated electronic, transport, and related properties of zinc blende boron arsenide (zb-BAs)

DOE PAGES

Nwigboji, Ifeanyi H.; Malozovsky, Yuriy; Franklin, Lashounda; ...

2016-10-11

Here, we present the results from ab-initio, self-consistent density functional theory (DFT) calculations of electronic, transport, and bulk properties of zinc blende boron arsenide. We utilized the local density approximation potential of Ceperley and Alder, as parameterized by Vosko and his group, the linear combination of Gaussian orbitals formalism, and the Bagayoko, Zhao, and Williams (BZW) method, as enhanced by Ekuma and Franklin (BZW-EF), in carrying out our completely self-consistent calculations. With this method, the results of our calculations have the full, physical content of density functional theory (DFT). Our results include electronic energy bands, densities of states, effective masses,more » and the bulk modulus. Our calculated, indirect band gap of 1.48 eV, from C to a conduction band minimum close to X, for the room temperature lattice constant of 4.777 Å, is in an excellent agreement with the experimental value of 1.46 6 0.02 eV. We thor-oughly explain the reasons for the excellent agreement between our findings and corresponding, experimental ones. This work provides a confirmation of the capability of DFT to describe accu-rately properties of materials, provides a confirmation of the capability of DFT to describe accu-rately properties of materials, if the computations adhere strictly to the conditions of validity of DFT, as done by the BZW-EF method.« less

Strong interplay between structure and electronic properties in CuIn(S,Se){2}: a first-principles study.

PubMed

Vidal, Julien; Botti, Silvana; Olsson, Pär; Guillemoles, Jean-François; Reining, Lucia

2010-02-05

We present a first-principles study of the electronic properties of CuIn(S,Se){2} (CIS) using state-of-the-art self-consistent GW and hybrid functionals. The calculated band gap depends strongly on the anion displacement u, an internal structural parameter that measures lattice distortion. This contrasts with the observed stability of the band gap of CIS solar panels under operating conditions, where a relatively large dispersion of values for u occurs. We solve this apparent paradox considering the coupled effect on the band gap of copper vacancies and lattice distortions. The correct treatment of d electrons in these materials requires going beyond density functional theory, and GW self-consistency is critical to evaluate the quasiparticle gap and the valence band maximum.

Self-Consistent Charge Density Functional Tight-Binding Study of Poly(3,4-ethylenedioxythiophene): Poly(styrenesulfonate) Ammonia Gas Sensor.

PubMed

Marutaphan, Ampaiwan; Seekaew, Yotsarayuth; Wongchoosuk, Chatchawal

2017-12-01

Geometric and electronic properties of 3,4-ethylenedioxythiophene (EDOT), styrene sulfonate (SS), and EDOT: SS oligomers up to 10 repeating units were studied by the self-consistent charge density functional tight-binding (SCC-DFTB) method. An application of PEDOT:PSS for ammonia (NH 3 ) detection was highlighted and investigated both experimentally and theoretically. The results showed an important role of H-bonds in EDOT:SS oligomers complex conformation. Electrical conductivity of EDOT increased with increasing oligomers and doping SS due to enhancement of π conjugation. Printed PEDOT:PSS gas sensor exhibited relatively high response and selectivity to NH 3 . The SCC-DFTB calculation suggested domination of direct charge transfer process in changing of PEDOT:PSS conductivity upon NH 3 exposure at room temperature. The NH 3 molecules preferred to bind with PEDOT:PSS via physisorption. The most favorable adsorption site for PEDOT:PSS-NH 3 interaction was found to be at the nitrogen atom of NH 3 and hydrogen atoms of SS with an average optimal binding distance of 2.00 Å.

Picosecond time-resolved measurements of dense plasma line shifts

DOE PAGES

Stillman, C. R.; Nilson, P. M.; Ivancic, S. T.; ...

2017-06-13

Picosecond time-resolved x-ray spectroscopy is used to measure the spectral line shift of the 1s2p–1s 2 transition in He-like Al ions as a function of the instantaneous plasma conditions. The plasma temperature and density are inferred from the Al He α complex using a nonlocal-thermodynamic-equilibrium atomic physics model. The experimental spectra show a linearly increasing red shift for electron densities of 1 to 5 × 10 23 cm –3. Furthermore, the measured line shifts are broadly consistent with a generalized analytic line-shift model based on calculations of a self-consistent field ion sphere model.

Picosecond time-resolved measurements of dense plasma line shifts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stillman, C. R.; Nilson, P. M.; Ivancic, S. T.

Picosecond time-resolved x-ray spectroscopy is used to measure the spectral line shift of the 1s2p–1s 2 transition in He-like Al ions as a function of the instantaneous plasma conditions. The plasma temperature and density are inferred from the Al He α complex using a nonlocal-thermodynamic-equilibrium atomic physics model. The experimental spectra show a linearly increasing red shift for electron densities of 1 to 5 × 10 23 cm –3. Furthermore, the measured line shifts are broadly consistent with a generalized analytic line-shift model based on calculations of a self-consistent field ion sphere model.

Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs

DOE PAGES

Filatov, Michael; Liu, Fang; Kim, Kwang S.; ...

2016-12-22

Here, the spin-restricted ensemble-referenced Kohn-Sham (REKS) method is based on an ensemble representation of the density and is capable of correctly describing the non-dynamic electron correlation stemming from (near-)degeneracy of several electronic configurations. The existing REKS methodology describes systems with two electrons in two fractionally occupied orbitals. In this work, the REKS methodology is extended to treat systems with four fractionally occupied orbitals accommodating four electrons and self-consistent implementation of the REKS(4,4) method with simultaneous optimization of the orbitals and their fractional occupation numbers is reported. The new method is applied to a number of molecular systems where simultaneous dissociationmore » of several chemical bonds takes place, as well as to the singlet ground states of organic tetraradicals 2,4-didehydrometaxylylene and 1,4,6,9-spiro[4.4]nonatetrayl.« less

Effect of EMIC Wave Normal Angle Distribution on Relativistic Electron Scattering Based on the Newly Developed Self-consistent RC/EMIC Waves Model by Khazanov et al. [2006

NASA Technical Reports Server (NTRS)

Khazanov, G. V.; Gallagher, D. L.; Gamayunov, K.

2007-01-01

It is well known that the effects of EMIC waves on RC ion and RB electron dynamics strongly depend on such particle/wave characteristics as the phase-space distribution function, frequency, wave-normal angle, wave energy, and the form of wave spectral energy density. Therefore, realistic characteristics of EMIC waves should be properly determined by modeling the RC-EMIC waves evolution self-consistently. Such a selfconsistent model progressively has been developing by Khaznnov et al. [2002-2006]. It solves a system of two coupled kinetic equations: one equation describes the RC ion dynamics and another equation describes the energy density evolution of EMIC waves. Using this model, we present the effectiveness of relativistic electron scattering and compare our results with previous work in this area of research.

Beyond the random-phase approximation for the electron correlation energy: the importance of single excitations.

PubMed

Ren, Xinguo; Tkatchenko, Alexandre; Rinke, Patrick; Scheffler, Matthias

2011-04-15

The random-phase approximation (RPA) for the electron correlation energy, combined with the exact-exchange (EX) energy, represents the state-of-the-art exchange-correlation functional within density-functional theory. However, the standard RPA practice--evaluating both the EX and the RPA correlation energies using Kohn-Sham (KS) orbitals from local or semilocal exchange-correlation functionals--leads to a systematic underbinding of molecules and solids. Here we demonstrate that this behavior can be corrected by adding a "single excitation" contribution, so far not included in the standard RPA scheme. A similar improvement can also be achieved by replacing the non-self-consistent EX total energy by the corresponding self-consistent Hartree-Fock total energy, while retaining the RPA correlation energy evaluated using KS orbitals. Both schemes achieve chemical accuracy for a standard benchmark set of noncovalent intermolecular interactions.

DYNAMICS OF SELF-GRAVITY WAKES IN DENSE PLANETARY RINGS. I. PITCH ANGLE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michikoshi, Shugo; Kokubo, Eiichiro; Fujii, Akihiko

2015-10-20

We investigate the dynamics of self-gravity wakes in dense planetary rings. In particular, we examine how the pitch angles of self-gravity wakes depend on ring parameters using N-body simulations. We calculate the pitch angles using the two-dimensional autocorrelation function of the ring surface density. We obtain the pitch angles for the inner and outer parts of the autocorrelation function separately. We confirm that the pitch angles are 15°–30° for reasonable ring parameters, which are consistent with previous studies. We find that the inner pitch angle increases with the Saturnicentric distance, while it barely depends on the optical depth and themore » restitution coefficient of ring particles. The increase of the inner pitch angle with the Saturnicentric distance is consistent with the observations of the A ring. The outer pitch angle does not have a clear dependence on any ring parameters and is about 10°–15°. This value is consistent with the pitch angle of spiral arms in collisionless systems.« less

Extended screened exchange functional derived from transcorrelated density functional theory.

PubMed

Umezawa, Naoto

2017-09-14

We propose a new formulation of the correlation energy functional derived from the transcorrelated method in use in density functional theory (TC-DFT). An effective Hamiltonian, H TC , is introduced by a similarity transformation of a many-body Hamiltonian, H, with respect to a complex function F: H TC =1FHF. It is proved that an expectation value of H TC for a normalized single Slater determinant, D n , corresponds to the total energy: E[n] = ⟨Ψ n |H|Ψ n ⟩/⟨Ψ n |Ψ n ⟩ = ⟨D n |H TC |D n ⟩ under the two assumptions: (1) The electron density nr associated with a trial wave function Ψ n = D n F is v-representable and (2) Ψ n and D n give rise to the same electron density nr. This formulation, therefore, provides an alternative expression of the total energy that is useful for the development of novel correlation energy functionals. By substituting a specific function for F, we successfully derived a model correlation energy functional, which resembles the functional form of the screened exchange method. The proposed functional, named the extended screened exchange (ESX) functional, is described within two-body integrals and is parametrized for a numerically exact correlation energy of the homogeneous electron gas. The ESX functional does not contain any ingredients of (semi-)local functionals and thus is totally free from self-interactions. The computational cost for solving the self-consistent-field equation is comparable to that of the Hartree-Fock method. We apply the ESX functional to electronic structure calculations for a solid silicon, H - ion, and small atoms. The results demonstrate that the TC-DFT formulation is promising for the systematic improvement of the correlation energy functional.

Orthogonality of embedded wave functions for different states in frozen-density embedding theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zech, Alexander; Wesolowski, Tomasz A.; Aquilante, Francesco

2015-10-28

Other than lowest-energy stationary embedded wave functions obtained in Frozen-Density Embedding Theory (FDET) [T. A. Wesolowski, Phys. Rev. A 77, 012504 (2008)] can be associated with electronic excited states but they can be mutually non-orthogonal. Although this does not violate any physical principles — embedded wave functions are only auxiliary objects used to obtain stationary densities — working with orthogonal functions has many practical advantages. In the present work, we show numerically that excitation energies obtained using conventional FDET calculations (allowing for non-orthogonality) can be obtained using embedded wave functions which are strictly orthogonal. The used method preserves the mathematicalmore » structure of FDET and self-consistency between energy, embedded wave function, and the embedding potential (they are connected through the Euler-Lagrange equations). The orthogonality is built-in through the linearization in the embedded density of the relevant components of the total energy functional. Moreover, we show formally that the differences between the expectation values of the embedded Hamiltonian are equal to the excitation energies, which is the exact result within linearized FDET. Linearized FDET is shown to be a robust approximation for a large class of reference densities.« less

Self-consistent fluid modeling and simulation on a pulsed microwave atmospheric-pressure argon plasma jet

NASA Astrophysics Data System (ADS)

Chen, Zhaoquan; Yin, Zhixiang; Chen, Minggong; Hong, Lingli; Xia, Guangqing; Hu, Yelin; Huang, Yourui; Liu, Minghai; Kudryavtsev, A. A.

2014-10-01

In present study, a pulsed lower-power microwave-driven atmospheric-pressure argon plasma jet has been introduced with the type of coaxial transmission line resonator. The plasma jet plume is with room air temperature, even can be directly touched by human body without any hot harm. In order to study ionization process of the proposed plasma jet, a self-consistent hybrid fluid model is constructed in which Maxwell's equations are solved numerically by finite-difference time-domain method and a fluid model is used to study the characteristics of argon plasma evolution. With a Guass type input power function, the spatio-temporal distributions of the electron density, the electron temperature, the electric field, and the absorbed power density have been simulated, respectively. The simulation results suggest that the peak values of the electron temperature and the electric field are synchronous with the input pulsed microwave power but the maximum quantities of the electron density and the absorbed power density are lagged to the microwave power excitation. In addition, the pulsed plasma jet excited by the local enhanced electric field of surface plasmon polaritons should be the discharge mechanism of the proposed plasma jet.

Time-dependent density-functional tight-binding method with the third-order expansion of electron density

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nishimoto, Yoshio, E-mail: nishimoto.yoshio@fukui.kyoto-u.ac.jp

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 themore » 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.« less

Time-dependent density-functional tight-binding method with the third-order expansion of electron density.

PubMed

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.

Theory and Simulation of Self- and Mutual-Diffusion of Carrier Density and Temperature in Semiconductor Lasers

NASA Technical Reports Server (NTRS)

Li, Jian-Zhong; Cheung, Samson H.; Ning, C. Z.

2001-01-01

Carrier diffusion and thermal conduction play a fundamental role in the operation of high-power, broad-area semiconductor lasers. Restricted geometry, high pumping level and dynamic instability lead to inhomogeneous spatial distribution of plasma density, temperature, as well as light field, due to strong light-matter interaction. Thus, modeling and simulation of such optoelectronic devices rely on detailed descriptions of carrier dynamics and energy transport in the system. A self-consistent description of lasing and heating in large-aperture, inhomogeneous edge- or surface-emitting lasers (VCSELs) require coupled diffusion equations for carrier density and temperature. In this paper, we derive such equations from the Boltzmann transport equation for the carrier distributions. The derived self- and mutual-diffusion coefficients are in general nonlinear functions of carrier density and temperature including many-body interactions. We study the effects of many-body interactions on these coefficients, as well as the nonlinearity of these coefficients for large-area VCSELs. The effects of mutual diffusions on carrier and temperature distributions in gain-guided VCSELs will be also presented.

Tango

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parker, Jeffrey

Tango enables the accelerated numerical solution of the multiscale problem of self-consistent transport and turbulence. Fast turbulence results in fluxes of heat and particles that slowly change the mean profiles of temperature and density. The fluxes are computed by separate turbulence simulation codes; Tang solves for the self-consistent change in mean temperature or density given those fluxes.

Total-energy Assisted Tight-binding Method Based on Local Density Approximation of Density Functional Theory

NASA Astrophysics Data System (ADS)

Fujiwara, Takeo; Nishino, Shinya; Yamamoto, Susumu; Suzuki, Takashi; Ikeda, Minoru; Ohtani, Yasuaki

2018-06-01

A novel tight-binding method is developed, based on the extended Hückel approximation and charge self-consistency, with referring the band structure and the total energy of the local density approximation of the density functional theory. The parameters are so adjusted by computer that the result reproduces the band structure and the total energy, and the algorithm for determining parameters is established. The set of determined parameters is applicable to a variety of crystalline compounds and change of lattice constants, and, in other words, it is transferable. Examples are demonstrated for Si crystals of several crystalline structures varying lattice constants. Since the set of parameters is transferable, the present tight-binding method may be applicable also to molecular dynamics simulations of large-scale systems and long-time dynamical processes.

Effect of heroin-conditioned auditory stimuli on cerebral functional activity in rats

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trusk, T.C.; Stein, E.A.

1988-08-01

Cerebral functional activity was measured as changes in distribution of the free fatty acid (1-14C)octanoate in autoradiograms obtained from rats during brief presentation of a tone previously paired to infusions of heroin or saline. Rats were trained in groups of three consisting of one heroin self-administering animal and two animals receiving yoked infusions of heroin or saline. Behavioral experiments in separate groups of rats demonstrated that these training parameters imparts secondary reinforcing properties to the tone for animals self-administering heroin while the tone remains behaviorally neutral in yoked-infusion animals. The optical densities of thirty-seven brain regions were normalized to amore » relative index for comparisons between groups. Previous pairing of the tone to heroin infusions irrespective of behavior (yoked-heroin vs. yoked-saline groups) produced functional activity changes in fifteen brain areas. In addition, nineteen regional differences in octanoate labeling density were evident when comparison was made between animals previously trained to self-administer heroin to those receiving yoked-heroin infusions, while twelve differences were noted when comparisons were made between the yoked vehicle and self administration group. These functional activity changes are presumed related to the secondary reinforcing capacity of the tone acquired by association with heroin, and may identify neural substrates involved in auditory signalled conditioning of positive reinforcement to opiates.« less

Many-body Green’s function theory for electron-phonon interactions: Ground state properties of the Holstein dimer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Säkkinen, Niko; Leeuwen, Robert van; Peng, Yang

2015-12-21

We study ground-state properties of a two-site, two-electron Holstein model describing two molecules coupled indirectly via electron-phonon interaction by using both exact diagonalization and self-consistent diagrammatic many-body perturbation theory. The Hartree and self-consistent Born approximations used in the present work are studied at different levels of self-consistency. The governing equations are shown to exhibit multiple solutions when the electron-phonon interaction is sufficiently strong, whereas at smaller interactions, only a single solution is found. The additional solutions at larger electron-phonon couplings correspond to symmetry-broken states with inhomogeneous electron densities. A comparison to exact results indicates that this symmetry breaking is stronglymore » correlated with the formation of a bipolaron state in which the two electrons prefer to reside on the same molecule. The results further show that the Hartree and partially self-consistent Born solutions obtained by enforcing symmetry do not compare well with exact energetics, while the fully self-consistent Born approximation improves the qualitative and quantitative agreement with exact results in the same symmetric case. This together with a presented natural occupation number analysis supports the conclusion that the fully self-consistent approximation describes partially the bipolaron crossover. These results contribute to better understanding how these approximations cope with the strong localizing effect of the electron-phonon interaction.« less

A density matrix-based method for the linear-scaling calculation of dynamic second- and third-order properties at the Hartree-Fock and Kohn-Sham density functional theory levels.

PubMed

Kussmann, Jörg; Ochsenfeld, Christian

2007-11-28

A density matrix-based time-dependent self-consistent field (D-TDSCF) method for the calculation of dynamic polarizabilities and first hyperpolarizabilities using the Hartree-Fock and Kohn-Sham density functional theory approaches is presented. The D-TDSCF method allows us to reduce the asymptotic scaling behavior of the computational effort from cubic to linear for systems with a nonvanishing band gap. The linear scaling is achieved by combining a density matrix-based reformulation of the TDSCF equations with linear-scaling schemes for the formation of Fock- or Kohn-Sham-type matrices. In our reformulation only potentially linear-scaling matrices enter the formulation and efficient sparse algebra routines can be employed. Furthermore, the corresponding formulas for the first hyperpolarizabilities are given in terms of zeroth- and first-order one-particle reduced density matrices according to Wigner's (2n+1) rule. The scaling behavior of our method is illustrated for first exemplary calculations with systems of up to 1011 atoms and 8899 basis functions.

Extension of the Kohn-Sham formulation of density functional theory to finite temperature

DOE PAGES

Gonis, A.; Dane, M.

2017-12-20

Based on Mermin's extension of the Hohenberg and Kohn theorems to non-zero temperature, the Kohn-Sham formulation of density functional theory (KS-DFT) is generalized to finite temperature. Here, we show that present formulations are inconsistent with Mermin's functional containing expressions, in particular describing the Coulomb energy, that defy derivation and are even in violation of rules of logical inference. More; current methodology is in violation of fundamental laws of both quantum and classical mechanics. Based on this feature, we demonstrate the impossibility of extending the KS formalism to finite temperature through the self-consistent solutions of the single-particle Schrödinger equation of T>0.more » Guided by the form of Mermin's functional that depends on the eigenstates of a Hamiltonian, determined at T>0 we base our extension of KS-DFT on the determination of the excited states of a non-interacting system at the zero of temperature. The resulting formulation is consistent with that of Mermin constructing the free energy at T>0 in terms of the excited states of a non-interacting Hamiltonian (system) that, within the KS formalism, are described by Slater determinants. To determine the excited states at T=0 use is made of the extension of the Hohenberg and Kohn theorems to excited states presented in previous work applied here to a non-interacting collection of replicas of a non-interacting N-particle system, whose ground state density is taken to match that of K non-interacting replicas of an interacting N-particle system at T>0. The formalism allows for an ever denser population of the excitation spectrum of a Hamiltonian, within the KS approximation. The form of the auxiliary potential, (Kohn-Sham potential), is formally identical to that in the ground state formalism with the contribution of the Coulomb energy provided by the derivative of the Coulomb energy in all excited states taken into account. Once the excited states are determined, the minimum of the free energy within the KS formalism follows immediately in the form of Mermin's functional, but with the exact excited states in that functional represented by Slater determinants obtained through self-consistency conditions at the zero of temperature. Lastly, it is emphasized that, in departure from all existing formulations, no self-consistency conditions are implemented at finite T; as we show, in fact, such formulations are rigorously blocked.« less

Extension of the Kohn-Sham formulation of density functional theory to finite temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gonis, A.; Dane, M.

Based on Mermin's extension of the Hohenberg and Kohn theorems to non-zero temperature, the Kohn-Sham formulation of density functional theory (KS-DFT) is generalized to finite temperature. Here, we show that present formulations are inconsistent with Mermin's functional containing expressions, in particular describing the Coulomb energy, that defy derivation and are even in violation of rules of logical inference. More; current methodology is in violation of fundamental laws of both quantum and classical mechanics. Based on this feature, we demonstrate the impossibility of extending the KS formalism to finite temperature through the self-consistent solutions of the single-particle Schrödinger equation of T>0.more » Guided by the form of Mermin's functional that depends on the eigenstates of a Hamiltonian, determined at T>0 we base our extension of KS-DFT on the determination of the excited states of a non-interacting system at the zero of temperature. The resulting formulation is consistent with that of Mermin constructing the free energy at T>0 in terms of the excited states of a non-interacting Hamiltonian (system) that, within the KS formalism, are described by Slater determinants. To determine the excited states at T=0 use is made of the extension of the Hohenberg and Kohn theorems to excited states presented in previous work applied here to a non-interacting collection of replicas of a non-interacting N-particle system, whose ground state density is taken to match that of K non-interacting replicas of an interacting N-particle system at T>0. The formalism allows for an ever denser population of the excitation spectrum of a Hamiltonian, within the KS approximation. The form of the auxiliary potential, (Kohn-Sham potential), is formally identical to that in the ground state formalism with the contribution of the Coulomb energy provided by the derivative of the Coulomb energy in all excited states taken into account. Once the excited states are determined, the minimum of the free energy within the KS formalism follows immediately in the form of Mermin's functional, but with the exact excited states in that functional represented by Slater determinants obtained through self-consistency conditions at the zero of temperature. Lastly, it is emphasized that, in departure from all existing formulations, no self-consistency conditions are implemented at finite T; as we show, in fact, such formulations are rigorously blocked.« less

Excitation spectra of retinal by multiconfiguration pair-density functional theory.

PubMed

Dong, Sijia S; Gagliardi, Laura; Truhlar, Donald G

2018-03-07

Retinal is the chromophore in proteins responsible for vision. The absorption maximum of retinal is sensitive to mutations of the protein. However, it is not easy to predict the absorption spectrum of retinal accurately, and questions remain even after intensive investigation. Retinal poses a challenge for Kohn-Sham density functional theory (KS-DFT) because of the charge transfer character in its excitations, and it poses a challenge for wave function theory because the large size of the molecule makes multiconfigurational perturbation theory methods expensive. In this study, we demonstrate that multiconfiguration pair-density functional theory (MC-PDFT) provides an efficient way to predict the vertical excitation energies of 11-Z retinal, and it reproduces the experimentally determined absorption band widths and peak positions better than complete active space second-order perturbation theory (CASPT2). The consistency between complete active space self-consistent field (CASSCF) and KS-DFT dipole moments is demonstrated to be a useful criterion in selecting the active space. We also found that the nature of the terminal groups and the conformations of retinal play a significant role in the absorption spectrum. By considering a thermal distribution of conformations, we predict an absorption spectrum of retinal that is consistent with the experimental gas-phase spectrum. The location of the absorption peak and the spectral broadening based on MC-PDFT calculations agree better with experiments than those of CASPT2.

Adhesion of a bimetallic interface. Ph.D. Thesis - Case Western Reserve Univ.; [for Al, Mg, and Zn

NASA Technical Reports Server (NTRS)

Ferrante, J.

1978-01-01

The Hohenberg-Kohn and Kohn-Sham formalisms are used to examine binding (binding energy as a function of separation) for combinations of the simple metals Al(111), Zn(0001), Mg(0001), and Na(110) in contact. Similar metal contacts between Al, Zn, Mg, and Na are examined self-consistently in an ab initio calculation using the Kohn-Sham formalism. Crystallinity is included using the Aschroft pseudopotential via first order perturbation theory for the electron-ion interaction; and the ion-ion interaction is included exactly via a lattice sum. Binding energy was determined both in the local-density approximation and including gradient corrections to the exchange and correlation energy. Binding was found in all cases. In dissimilar metal contacts, interfacial bonding was greater than that in the weaker material predicting the possibility of metallic transfer. The nonzero position of the energy minimum in like metal contacts is explained in terms of consistency between the Ashcroft pseudopotential and the bulk charge density. Good agreement with experimental surface energies is obtained in the self-consistent calculation when nonlocal terms are included.

Multiconfiguration pair-density functional theory: barrier heights and main group and transition metal energetics.

PubMed

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.

Multiconfiguration Pair-Density Functional Theory.

PubMed

Li Manni, Giovanni; Carlson, Rebecca K; Luo, Sijie; Ma, Dongxia; Olsen, Jeppe; Truhlar, Donald G; Gagliardi, Laura

2014-09-09

We present a new theoretical framework, called Multiconfiguration Pair-Density Functional Theory (MC-PDFT), which combines multiconfigurational wave functions with a generalization of density functional theory (DFT). A multiconfigurational self-consistent-field (MCSCF) wave function with correct spin and space symmetry is used to compute the total electronic density, its gradient, the on-top pair density, and the kinetic and Coulomb contributions to the total electronic energy. We then use a functional of the total density, its gradient, and the on-top pair density to calculate the remaining part of the energy, which we call the on-top-density-functional energy in contrast to the exchange-correlation energy of Kohn-Sham DFT. Because the on-top pair density is an element of the two-particle density matrix, this goes beyond the Hohenberg-Kohn theorem that refers only to the one-particle density. To illustrate the theory, we obtain first approximations to the required new type of density functionals by translating conventional density functionals of the spin densities using a simple prescription, and we perform post-SCF density functional calculations using the total density, density gradient, and on-top pair density from the MCSCF calculations. Double counting of dynamic correlation or exchange does not occur because the MCSCF energy is not used. The theory is illustrated by applications to the bond energies and potential energy curves of H2, N2, F2, CaO, Cr2, and NiCl and the electronic excitation energies of Be, C, N, N(+), O, O(+), Sc(+), Mn, Co, Mo, Ru, N2, HCHO, C4H6, c-C5H6, and pyrazine. The method presented has a computational cost and scaling similar to MCSCF, but a quantitative accuracy, even with the present first approximations to the new types of density functionals, that is comparable to much more expensive multireference perturbation theory methods.

Characterization of Thin Film Materials using SCAN meta-GGA, an Accurate Nonempirical Density Functional

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buda, I. G.; Lane, C.; Barbiellini, B.

We discuss self-consistently obtained ground-state electronic properties of monolayers of graphene and a number of ’beyond graphene’ compounds, including films of transition-metal dichalcogenides (TMDs), using the recently proposed strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation (meta-GGA) to the density functional theory. The SCAN meta-GGA results are compared with those based on the local density approximation (LDA) as well as the generalized gradient approximation (GGA). As expected, the GGA yields expanded lattices and softened bonds in relation to the LDA, but the SCAN meta-GGA systematically improves the agreement with experiment. Our study suggests the efficacy of the SCAN functionalmore » for accurate modeling of electronic structures of layered materials in high-throughput calculations more generally.« less

Projected quasiparticle theory for molecular electronic structure

NASA Astrophysics Data System (ADS)

Scuseria, Gustavo E.; Jiménez-Hoyos, Carlos A.; Henderson, Thomas M.; Samanta, Kousik; Ellis, Jason K.

2011-09-01

We derive and implement symmetry-projected Hartree-Fock-Bogoliubov (HFB) equations and apply them to the molecular electronic structure problem. All symmetries (particle number, spin, spatial, and complex conjugation) are deliberately broken and restored in a self-consistent variation-after-projection approach. We show that the resulting method yields a comprehensive black-box treatment of static correlations with effective one-electron (mean-field) computational cost. The ensuing wave function is of multireference character and permeates the entire Hilbert space of the problem. The energy expression is different from regular HFB theory but remains a functional of an independent quasiparticle density matrix. All reduced density matrices are expressible as an integration of transition density matrices over a gauge grid. We present several proof-of-principle examples demonstrating the compelling power of projected quasiparticle theory for quantum chemistry.

Band-gap corrected density functional theory calculations for InAs/GaSb type II superlattices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jianwei; Zhang, Yong

2014-12-07

We performed pseudopotential based density functional theory (DFT) calculations for GaSb/InAs type II superlattices (T2SLs), with bandgap errors from the local density approximation mitigated by applying an empirical method to correct the bulk bandgaps. Specifically, this work (1) compared the calculated bandgaps with experimental data and non-self-consistent atomistic methods; (2) calculated the T2SL band structures with varying structural parameters; (3) investigated the interfacial effects associated with the no-common-atom heterostructure; and (4) studied the strain effect due to lattice mismatch between the two components. This work demonstrates the feasibility of applying the DFT method to more exotic heterostructures and defect problemsmore » related to this material system.« less

Characterization of Thin Film Materials using SCAN meta-GGA, an Accurate Nonempirical Density Functional

DOE PAGES

Buda, I. G.; Lane, C.; Barbiellini, B.; ...

2017-03-23

We discuss self-consistently obtained ground-state electronic properties of monolayers of graphene and a number of ’beyond graphene’ compounds, including films of transition-metal dichalcogenides (TMDs), using the recently proposed strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation (meta-GGA) to the density functional theory. The SCAN meta-GGA results are compared with those based on the local density approximation (LDA) as well as the generalized gradient approximation (GGA). As expected, the GGA yields expanded lattices and softened bonds in relation to the LDA, but the SCAN meta-GGA systematically improves the agreement with experiment. Our study suggests the efficacy of the SCAN functionalmore » for accurate modeling of electronic structures of layered materials in high-throughput calculations more generally.« less

Systematic theoretical investigation of the zero-field splitting in Gd(III) complexes: Wave function and density functional approaches

NASA Astrophysics Data System (ADS)

Khan, Shehryar; Kubica-Misztal, Aleksandra; Kruk, Danuta; Kowalewski, Jozef; Odelius, Michael

2015-01-01

The zero-field splitting (ZFS) of the electronic ground state in paramagnetic ions is a sensitive probe of the variations in the electronic and molecular structure with an impact on fields ranging from fundamental physical chemistry to medical applications. A detailed analysis of the ZFS in a series of symmetric Gd(III) complexes is presented in order to establish the applicability and accuracy of computational methods using multiconfigurational complete-active-space self-consistent field wave functions and of density functional theory calculations. The various computational schemes are then applied to larger complexes Gd(III)DOTA(H2O)-, Gd(III)DTPA(H2O)2-, and Gd(III)(H2O)83+ in order to analyze how the theoretical results compare to experimentally derived parameters. In contrast to approximations based on density functional theory, the multiconfigurational methods produce results for the ZFS of Gd(III) complexes on the correct order of magnitude.

Nonequilibrium electromagnetics: Local and macroscopic fields and constitutive relationships

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker-Jarvis, James; Kabos, Pavel; Holloway, Christopher L.

We study the electrodynamics of materials using a Liouville-Hamiltonian-based statistical-mechanical theory. Our goal is to develop electrodynamics from an ensemble-average viewpoint that is valid for microscopic and nonequilibrium systems at molecular to submolecular scales. This approach is not based on a Taylor series expansion of the charge density to obtain the multipoles. Instead, expressions of the molecular multipoles are used in an inverse problem to obtain the averaging statistical-density function that is used to obtain the macroscopic fields. The advantages of this method are that the averaging function is constructed in a self-consistent manner and the molecules can either bemore » treated as point multipoles or contain more microstructure. Expressions for the local and macroscopic fields are obtained, and evolution equations for the constitutive parameters are developed. We derive equations for the local field as functions of the applied, polarization, magnetization, strain density, and macroscopic fields.« less

A thermally self-sustained micro-power plant with integrated micro-solid oxide fuel cells, micro-reformer and functional micro-fluidic carrier

NASA Astrophysics Data System (ADS)

Scherrer, Barbara; Evans, Anna; Santis-Alvarez, Alejandro J.; Jiang, Bo; Martynczuk, Julia; Galinski, Henning; Nabavi, Majid; Prestat, Michel; Tölke, René; Bieberle-Hütter, Anja; Poulikakos, Dimos; Muralt, Paul; Niedermann, Philippe; Dommann, Alex; Maeder, Thomas; Heeb, Peter; Straessle, Valentin; Muller, Claude; Gauckler, Ludwig J.

2014-07-01

Low temperature micro-solid oxide fuel cell (micro-SOFC) systems are an attractive alternative power source for small-size portable electronic devices due to their high energy efficiency and density. Here, we report on a thermally self-sustainable reformer-micro-SOFC assembly. The device consists of a micro-reformer bonded to a silicon chip containing 30 micro-SOFC membranes and a functional glass carrier with gas channels and screen-printed heaters for start-up. Thermal independence of the device from the externally powered heater is achieved by exothermic reforming reactions above 470 °C. The reforming reaction and the fuel gas flow rate of the n-butane/air gas mixture controls the operation temperature and gas composition on the micro-SOFC membrane. In the temperature range between 505 °C and 570 °C, the gas composition after the micro-reformer consists of 12 vol.% to 28 vol.% H2. An open-circuit voltage of 1.0 V and maximum power density of 47 mW cm-2 at 565 °C is achieved with the on-chip produced hydrogen at the micro-SOFC membranes.

Testing the nonlocal kinetic energy functional of an inhomogeneous, two-dimensional degenerate Fermi gas within the average density approximation

NASA Astrophysics Data System (ADS)

Towers, J.; van Zyl, B. P.; Kirkby, W.

2015-08-01

In a recent paper [B. P. van Zyl et al., Phys. Rev. A 89, 022503 (2014), 10.1103/PhysRevA.89.022503], the average density approximation (ADA) was implemented to develop a parameter-free, nonlocal kinetic energy functional to be used in the orbital-free density functional theory of an inhomogeneous, two-dimensional (2D) Fermi gas. In this work, we provide a detailed comparison of self-consistent calculations within the ADA with the exact results of the Kohn-Sham density functional theory and the elementary Thomas-Fermi (TF) approximation. We demonstrate that the ADA for the 2D kinetic energy functional works very well under a wide variety of confinement potentials, even for relatively small particle numbers. Remarkably, the TF approximation for the kinetic energy functional, without any gradient corrections, also yields good agreement with the exact kinetic energy for all confining potentials considered, although at the expense of the spatial and kinetic energy densities exhibiting poor pointwise agreement, particularly near the TF radius. Our findings illustrate that the ADA kinetic energy functional yields accurate results for both the local and global equilibrium properties of an inhomogeneous 2D Fermi gas, without the need for any fitting parameters.

Current Density Functional Theory Using Meta-Generalized Gradient Exchange-Correlation Functionals.

PubMed

Furness, James W; Verbeke, Joachim; Tellgren, Erik I; Stopkowicz, Stella; Ekström, Ulf; Helgaker, Trygve; Teale, Andrew M

2015-09-08

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.

Ensemble density variational methods with self- and ghost-interaction-corrected functionals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pastorczak, Ewa; Pernal, Katarzyna, E-mail: pernalk@gmail.com

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 introducedmore » 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.« less

Self-consistent mean-field approach to the statistical level density in spherical nuclei

NASA Astrophysics Data System (ADS)

Kolomietz, V. M.; Sanzhur, A. I.; Shlomo, S.

2018-06-01

A self-consistent mean-field approach within the extended Thomas-Fermi approximation with Skyrme forces is applied to the calculations of the statistical level density in spherical nuclei. Landau's concept of quasiparticles with the nucleon effective mass and the correct description of the continuum states for the finite-depth potentials are taken into consideration. The A dependence and the temperature dependence of the statistical inverse level-density parameter K is obtained in a good agreement with experimental data.

Semiempirical self-consistent polarization description of bulk water, the liquid-vapor interface, and cubic ice.

PubMed

Murdachaew, Garold; Mundy, Christopher J; Schenter, Gregory K; Laino, Teodoro; Hutter, Jürg

2011-06-16

We have applied an efficient electronic structure approach, the semiempirical self-consistent polarization neglect of diatomic differential overlap (SCP-NDDO) method, previously parametrized to reproduce properties of water clusters by Chang, Schenter, and Garrett [ J. Chem. Phys. 2008 , 128 , 164111 ] and now implemented in the CP2K package, to model ambient liquid water at 300 K (both the bulk and the liquid-vapor interface) and cubic ice at 15 and 250 K. The SCP-NDDO potential retains its transferability and good performance across the full range of conditions encountered in the clusters and the bulk phases of water. In particular, we obtain good results for the density, radial distribution functions, enthalpy of vaporization, self-diffusion coefficient, molecular dipole moment distribution, and hydrogen bond populations, in comparison to experimental measurements. © 2011 American Chemical Society

Nonlocal kinetic energy functionals by functional integration.

PubMed

Mi, Wenhui; Genova, Alessandro; Pavanello, Michele

2018-05-14

Since the seminal studies of Thomas and Fermi, researchers in the Density-Functional Theory (DFT) community are searching for accurate electron density functionals. Arguably, the toughest functional to approximate is the noninteracting kinetic energy, T s [ρ], the subject of this work. The typical paradigm is to first approximate the energy functional and then take its functional derivative, δT s [ρ]δρ(r), yielding a potential that can be used in orbital-free DFT or subsystem DFT simulations. Here, this paradigm is challenged by constructing the potential from the second-functional derivative via functional integration. A new nonlocal functional for T s [ρ] is prescribed [which we dub Mi-Genova-Pavanello (MGP)] having a density independent kernel. MGP is constructed to satisfy three exact conditions: (1) a nonzero "Kinetic electron" arising from a nonzero exchange hole; (2) the second functional derivative must reduce to the inverse Lindhard function in the limit of homogenous densities; (3) the potential is derived from functional integration of the second functional derivative. Pilot calculations show that MGP is capable of reproducing accurate equilibrium volumes, bulk moduli, total energy, and electron densities for metallic (body-centered cubic, face-centered cubic) and semiconducting (crystal diamond) phases of silicon as well as of III-V semiconductors. The MGP functional is found to be numerically stable typically reaching self-consistency within 12 iterations of a truncated Newton minimization algorithm. MGP's computational cost and memory requirements are low and comparable to the Wang-Teter nonlocal functional or any generalized gradient approximation functional.

Nonlocal kinetic energy functionals by functional integration

NASA Astrophysics Data System (ADS)

Mi, Wenhui; Genova, Alessandro; Pavanello, Michele

2018-05-01

Since the seminal studies of Thomas and Fermi, researchers in the Density-Functional Theory (DFT) community are searching for accurate electron density functionals. Arguably, the toughest functional to approximate is the noninteracting kinetic energy, Ts[ρ], the subject of this work. The typical paradigm is to first approximate the energy functional and then take its functional derivative, δ/Ts[ρ ] δ ρ (r ) , yielding a potential that can be used in orbital-free DFT or subsystem DFT simulations. Here, this paradigm is challenged by constructing the potential from the second-functional derivative via functional integration. A new nonlocal functional for Ts[ρ] is prescribed [which we dub Mi-Genova-Pavanello (MGP)] having a density independent kernel. MGP is constructed to satisfy three exact conditions: (1) a nonzero "Kinetic electron" arising from a nonzero exchange hole; (2) the second functional derivative must reduce to the inverse Lindhard function in the limit of homogenous densities; (3) the potential is derived from functional integration of the second functional derivative. Pilot calculations show that MGP is capable of reproducing accurate equilibrium volumes, bulk moduli, total energy, and electron densities for metallic (body-centered cubic, face-centered cubic) and semiconducting (crystal diamond) phases of silicon as well as of III-V semiconductors. The MGP functional is found to be numerically stable typically reaching self-consistency within 12 iterations of a truncated Newton minimization algorithm. MGP's computational cost and memory requirements are low and comparable to the Wang-Teter nonlocal functional or any generalized gradient approximation functional.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Popovich, P.; Carter, T. A.; Friedman, B.

Numerical simulation of plasma turbulence in the Large Plasma Device (LAPD) [W. Gekelman, H. Pfister, Z. Lucky et al., Rev. Sci. Instrum. 62, 2875 (1991)] is presented. The model, implemented in the BOUndary Turbulence code [M. Umansky, X. Xu, B. Dudson et al., Contrib. Plasma Phys. 180, 887 (2009)], includes three-dimensional (3D) collisional fluid equations for plasma density, electron parallel momentum, and current continuity, and also includes the effects of ion-neutral collisions. In nonlinear simulations using measured LAPD density profiles but assuming constant temperature profile for simplicity, self-consistent evolution of instabilities and nonlinearly generated zonal flows results in a saturatedmore » turbulent state. Comparisons of these simulations with measurements in LAPD plasmas reveal good qualitative and reasonable quantitative agreement, in particular in frequency spectrum, spatial correlation, and amplitude probability distribution function of density fluctuations. For comparison with LAPD measurements, the plasma density profile in simulations is maintained either by direct azimuthal averaging on each time step, or by adding particle source/sink function. The inferred source/sink values are consistent with the estimated ionization source and parallel losses in LAPD. These simulations lay the groundwork for more a comprehensive effort to test fluid turbulence simulation against LAPD data.« less

Combining Density Functional Theory and Green's Function Theory: Range-Separated, Nonlocal, Dynamic, and Orbital-Dependent Hybrid Functional.

PubMed

Kananenka, Alexei A; Zgid, Dominika

2017-11-14

We present a rigorous framework which combines single-particle Green's function theory with density functional theory based on a separation of electron-electron interactions into short- and long-range components. Short-range contribution to the total energy and exchange-correlation potential is provided by a density functional approximation, while the long-range contribution is calculated using an explicit many-body Green's function method. Such a hybrid results in a nonlocal, dynamic, and orbital-dependent exchange-correlation functional of a single-particle Green's function. In particular, we present a range-separated hybrid functional called srSVWN5-lrGF2 which combines the local-density approximation and the second-order Green's function theory. We illustrate that similarly to density functional approximations, the new functional is weakly basis-set dependent. Furthermore, it offers an improved description of the short-range dynamic correlation. The many-body contribution to the functional mitigates the many-electron self-interaction error present in many density functional approximations and provides a better description of molecular properties. Additionally, we illustrate that the new functional can be used to scale down the self-energy and, therefore, introduce an additional sparsity to the self-energy matrix that in the future can be exploited in calculations for large molecules or periodic systems.

Self-Interaction Error in Density Functional Theory: An Appraisal.

PubMed

Bao, Junwei Lucas; Gagliardi, Laura; Truhlar, Donald G

2018-05-03

Self-interaction error (SIE) is considered to be one of the major sources of error in most approximate exchange-correlation functionals for Kohn-Sham density-functional theory (KS-DFT), and it is large with all local exchange-correlation functionals and with some hybrid functionals. In this work, we consider systems conventionally considered to be dominated by SIE. For these systems, we demonstrate that by using multiconfiguration pair-density functional theory (MC-PDFT), the error of a translated local density-functional approximation is significantly reduced (by a factor of 3) when using an MCSCF density and on-top density, as compared to using KS-DFT with the parent functional; the error in MC-PDFT with local on-top functionals is even lower than the error in some popular KS-DFT hybrid functionals. Density-functional theory, either in MC-PDFT form with local on-top functionals or in KS-DFT form with some functionals having 50% or more nonlocal exchange, has smaller errors for SIE-prone systems than does CASSCF, which has no SIE.

Multiconfiguration Pair-Density Functional Theory: A New Way To Treat Strongly Correlated Systems.

PubMed

Gagliardi, Laura; Truhlar, Donald G; Li Manni, Giovanni; Carlson, Rebecca K; Hoyer, Chad E; Bao, Junwei Lucas

2017-01-17

The electronic energy of a system provides the Born-Oppenheimer potential energy for internuclear motion and thus determines molecular structure and spectra, bond energies, conformational energies, reaction barrier heights, and vibrational frequencies. The development of more efficient and more accurate ways to calculate the electronic energy of systems with inherently multiconfigurational electronic structure is essential for many applications, including transition metal and actinide chemistry, systems with partially broken bonds, many transition states, and most electronically excited states. Inherently multiconfigurational systems are called strongly correlated systems or multireference systems, where the latter name refers to the need for using more than one ("multiple") configuration state function to provide a good zero-order reference wave function. This Account describes multiconfiguration pair-density functional theory (MC-PDFT), which was developed as a way to combine the advantages of wave function theory (WFT) and density functional theory (DFT) to provide a better treatment of strongly correlated systems. First we review background material: the widely used Kohn-Sham DFT (which uses only a single Slater determinant as reference wave function), multiconfiguration WFT methods that treat inherently multiconfigurational systems based on an active space, and previous attempts to combine multiconfiguration WFT with DFT. Then we review the formulation of MC-PDFT. It is a generalization of Kohn-Sham DFT in that the electron kinetic energy and classical electrostatic energy are calculated from a reference wave function, while the rest of the energy is obtained from a density functional. However, there are two main differences with respent to Kohn-Sham DFT: (i) The reference wave function is multiconfigurational rather than being a single Slater determinant. (ii) The density functional is a function of the total density and the on-top pair density rather than being a function of the spin-up and spin-down densities. In work carried out so far, the multiconfigurational wave function is a multiconfiguration self-consistent-field wave function. The new formulation has the advantage that the reference wave function has the correct spatial and spin symmetry and can describe bond dissociation (of both single and multiple bonds) and electronic excitations in a formally and physically correct way. We then review the formulation of density functionals in terms of the on-top pair density. Finally we review successful applications of the theory to bond energies and bond dissociation potential energy curves of main-group and transition metal bonds, to barrier heights (including pericyclic reactions), to proton affinities, to the hydrogen bond energy of water dimer, to ground- and excited-state charge transfer, to valence and Rydberg excitations of molecules, and to singlet-triplet splittings of radicals. We find that that MC-PDFT can give accurate results not only with complete-active-space multiconfiguration wave functions but also with generalized-active-space multiconfiguration wave functions, which are practical for larger numbers of active electrons and active orbitals than are complete-active-space wave functions. The separated-pair approximation, which is a special case of generalized active space self-consistent-field theory, is especially promising. MC-PDFT, because it requires much less computer time and storage than pure WFT methods, has the potential to open larger and more complex strongly correlated systems to accurate simulation.

Self-Consistent Physical Properties of Carbon Nanotubes in Composite Materials

NASA Technical Reports Server (NTRS)

Pipes, R. B.; Frankland, S. J. V.; Hubert, P.; Saether, E.; Bushnell, Dennis M. (Technical Monitor)

2002-01-01

A set of relationships is developed for selected physical properties of single-walled carbon nanotubes (SWCN) and their hexagonal arrays as a function of nanotube size in terms of the chiral vector integer pair, (n,m). Properties include density, principal Young's modulus, and specific Young's modulus. Relationships between weight fraction and volume fraction of SWCN and their arrays are developed for polymeric mixtures.

Self-consistent one dimension in space and three dimension in velocity kinetic trajectory simulation model of magnetized plasma-wall transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chalise, Roshan, E-mail: plasma.roshan@gmail.com; Khanal, Raju

2015-11-15

We have developed a self-consistent 1d3v (one dimension in space and three dimension in velocity) Kinetic Trajectory Simulation (KTS) model, which can be used for modeling various situations of interest and yields results of high accuracy. Exact ion trajectories are followed, to calculate along them the ion distribution function, assuming an arbitrary injection ion distribution. The electrons, on the other hand, are assumed to have a cut-off Maxwellian velocity distribution at injection and their density distribution is obtained analytically. Starting from an initial guess, the potential profile is iterated towards the final time-independent self-consistent state. We have used it tomore » study plasma sheath region formed in presence of an oblique magnetic field. Our results agree well with previous works from other models, and hence, we expect our 1d3v KTS model to provide a basis for the studying of all types of magnetized plasmas, yielding more accurate results.« less

Ionic structures and transport properties of hot dense W and U plasmas

NASA Astrophysics Data System (ADS)

Hou, Yong; Yuan, Jianmin

2016-10-01

We have combined the average-atom model with the hyper-netted chain approximation (AAHNC) to describe the electronic and ionic structure of uranium and tungsten in the hot dense matter regime. When the electronic structure is described within the average-atom model, the effects of others ions on the electronic structure are considered by the correlation functions. And the ionic structure is calculated though using the hyper-netted chain (HNC) approximation. The ion-ion pair potential is calculated using the modified Gordon-Kim model based on the electronic density distribution in the temperature-depended density functional theory. And electronic and ionic structures are determined self-consistently. On the basis of the ion-ion pair potential, we perform the classical (CMD) and Langevin (LMD) molecular dynamics to simulate the ionic transport properties, such as ionic self-diffusion and shear viscosity coefficients, through the ionic velocity correlation functions. Due that the free electrons become more and more with increasing the plasma temperature, the influence of the electron-ion collisions on the transport properties become more and more important.

Excitation of turbulence by density waves

NASA Technical Reports Server (NTRS)

Tichen, C. M.

1985-01-01

A nonlinear system describes the microdynamical state of turbulence that is excited by density waves. It consists of an equation of propagation and a master equation. A group-scaling generates the scaled equations of many interacting groups of distribution functions. The two leading groups govern the transport processes of evolution and eddy diffusivity. The remaining sub-groups represent the relaxation for the approach of diffusivity to equilibrium. In strong turbulence, the sub-groups disperse themselves and the ensemble acts like a medium that offers an effective damping to close the hierarchy. The kinetic equation of turbulence is derived. It calculates the eddy viscosity and identifies the effective damping of the assumed medium self-consistently. It formulates the coupling mechanism for the intensification of the turbulent energy at the expense of the wave energy, and the transfer mechanism for the cascade. The spectra of velocity and density fluctuations find the power law k sup-2 and k sup-4, respectively.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Finzel, Kati, E-mail: kati.finzel@liu.se

The local conditions for the Pauli potential that are necessary in order to yield self-consistent electron densities from orbital-free calculations are investigated for approximations that are expressed with the help of a local position variable. It is shown that those local conditions also apply when the Pauli potential is given in terms of the electron density. An explicit formula for the Ne atom is given, preserving the local conditions during the iterative procedure. The resulting orbital-free electron density exhibits proper shell structure behavior and is in close agreement with the Kohn-Sham electron density. This study demonstrates that it is possiblemore » to obtain self-consistent orbital-free electron densities with proper atomic shell structure from simple one-point approximations for the Pauli potential at local density level.« less

Constraint on the second functional derivative of the exchange-correlation energy

NASA Astrophysics Data System (ADS)

Joubert, D. P.

2012-09-01

Using the density functional adiabatic connection approach for an N-electron system it is shown that ? γ is the coupling constant that scales the electron-electron interaction strength. For the non-interacting Kohn-Sham Hamiltonian γ = 0 and for the fully interacting system γ = 1. ? is the Hartree plus exchange-correlation energy while f 0(r) and fγ(r) are the Fukui functions of the non-interacting and interacting systems, respectively. This identity can serve to test the internal self-consistency or quality of approximate functionals. The quality of some popular approximate exchange and correlation functionals are tested for a simple model system.

PEVC-FMDF for Large Eddy Simulation of Compressible Turbulent Flows

NASA Astrophysics Data System (ADS)

Nouri Gheimassi, Arash; Nik, Mehdi; Givi, Peyman; Livescu, Daniel; Pope, Stephen

2017-11-01

The filtered density function (FDF) closure is extended to a ``self-contained'' format to include the subgrid scale (SGS) statistics of all of the hydro-thermo-chemical variables in turbulent flows. These are the thermodynamic pressure, the specific internal energy, the velocity vector, and the composition field. In this format, the model is comprehensive and facilitates large eddy simulation (LES) of flows at both low and high compressibility levels. A transport equation is developed for the joint ``pressure-energy-velocity-composition filtered mass density function (PEVC-FMDF).'' In this equation, the effect of convection appears in closed form. The coupling of the hydrodynamics and thermochemistry is modeled via a set of stochastic differential equation (SDE) for each of the transport variables. This yields a self-contained SGS closure. For demonstration, LES is conducted of a turbulent shear flow with transport of a passive scalar. The consistency of the PEVC-FMDF formulation is established, and its overall predictive capability is appraised via comparison with direct numerical simulation (DNS) data.

Crystal-field splittings in rare-earth-based hard magnets: An ab initio approach

NASA Astrophysics Data System (ADS)

Delange, Pascal; Biermann, Silke; Miyake, Takashi; Pourovskii, Leonid

2017-10-01

We apply the first-principles density functional theory + dynamical mean-field theory framework to evaluate the crystal-field splitting on rare-earth sites in hard magnetic intermetallics. An atomic (Hubbard-I) approximation is employed for local correlations on the rare-earth 4 f shell and self-consistency in the charge density is implemented. We reduce the density functional theory self-interaction contribution to the crystal-field splitting by properly averaging the 4 f charge density before recalculating the one-electron Kohn-Sham potential. Our approach is shown to reproduce the experimental crystal-field splitting in the prototypical rare-earth hard magnet SmCo5. Applying it to R Fe12 and R Fe12X hard magnets (R =Nd , Sm and X =N , Li), we obtain in particular a large positive value of the crystal-field parameter A20〈r2〉 in NdFe12N resulting in a strong out-of-plane anisotropy observed experimentally. The sign of A20〈r2〉 is predicted to be reversed by substituting N with Li, leading to a strong out-of-plane anisotropy in SmFe12Li . We discuss the origin of this strong impact of N and Li interstitials on the crystal-field splitting on rare-earth sites.

Multidimensional Skyrme-density-functional study of the spontaneous fission of 238U

DOE PAGES

Sadhukhan, J.; Mazurek, K.; Dobaczewski, J.; ...

2015-01-01

We determined the spontaneous fission lifetime of 238U by a minimization of the action integral in a three-dimensional space of collective variables. Apart from the mass-distribution multipole moments Q 20 (elongation) and Q 30 (left–right asymmetry), we also considered the pairing-fluctuation parameter λ 2 as a collective coordinate. The collective potential was obtained self-consistently using the Skyrme energy density functional SkM*. The inertia tensor was obtained within the nonperturbative cranking approximation to the adiabatic time-dependent Hartree–Fock–Bogoliubov approach. As a result, the pairing-fluctuation parameter λ 2 allowed us to control the pairing gap along the fission path, which significantly changed themore » spontaneous fission lifetime.« less

Structural and electronic properties of GaAs and GaP semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rani, Anita; Kumar, Ranjan

2015-05-15

The Structural and Electronic properties of Zinc Blende phase of GaAs and GaP compounds are studied using self consistent SIESTA-code, pseudopotentials and Density Functional Theory (DFT) in Local Density Approximation (LDA). The Lattice Constant, Equillibrium Volume, Cohesive Energy per pair, Compressibility and Band Gap are calculated. The band gaps calcultated with DFT using LDA is smaller than the experimental values. The P-V data fitted to third order Birch Murnaghan equation of state provide the Bulk Modulus and its pressure derivatives. Our Structural and Electronic properties estimations are in agreement with available experimental and theoretical data.

Bonding in the first-row diatomic molecules within the local spin-density approximation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Painter, G.S.; Averill, F.W.

1982-08-15

The Hohenberg-Kohn-Sham density-functional equations in the local spin-density approximation (LSDA) have been solved with essentially no loss of accuracy for dimers of the first row of the Periodic Table with the use of a fully-self-consistent spin-polarized Gaussian-orbital approach. Spectroscopic constants (binding energies, equilibrium separations, and ground-state vibrational frequencies) have been derived from the calculated potential-energy curves. Intercomparison of results obtained using the exchange-correlation functionals of Slater (scaled exchange or X..cap alpha..), Gunnarsson and Lundqvist (GL), and Vosko, Wilk, and Nusair (VWN) permits assessment of the relative merits of each and serves to identify general shortcomings in the LSDA. Basic trendsmore » are similar for each functional, but the treatment of the spin dependence of the exchange-correlation energy in the GL and VWN functionals yields a variation of the binding energy across the series which is more systematic than that in the X..cap alpha.. approximation. Agreement between the present results and those of Dunlap, Connolly, and Sabin in the X..cap alpha.., approximation confirms the accuracy of the variational charge-density-fit procedure used in the latter work. The refinements in correlation treatment within the VWN functional are reflected in improvements in binding energies which are only slight for most dimers in the series. This behavior is attributed to the error remaining in the exchange channel within the LSDA and demonstrates the necessity for self-interaction corrections for more accurate binding-energy determinations. Within the current LSDA, absolute accuracies of the VWN functional for the first-row dimers are within 2.3 eV for binding energies, 0.07 a.u. for bond lengths, and approx.200 cm/sup -1/ for vibrational frequencies.« less

Accurate density functional prediction of molecular electron affinity with the scaling corrected Kohn–Sham frontier orbital energies

NASA Astrophysics Data System (ADS)

Zhang, DaDi; Yang, Xiaolong; Zheng, Xiao; Yang, Weitao

2018-04-01

Electron affinity (EA) is the energy released when an additional electron is attached to an atom or a molecule. EA is a fundamental thermochemical property, and it is closely pertinent to other important properties such as electronegativity and hardness. However, accurate prediction of EA is difficult with density functional theory methods. The somewhat large error of the calculated EAs originates mainly from the intrinsic delocalisation error associated with the approximate exchange-correlation functional. In this work, we employ a previously developed non-empirical global scaling correction approach, which explicitly imposes the Perdew-Parr-Levy-Balduz condition to the approximate functional, and achieve a substantially improved accuracy for the calculated EAs. In our approach, the EA is given by the scaling corrected Kohn-Sham lowest unoccupied molecular orbital energy of the neutral molecule, without the need to carry out the self-consistent-field calculation for the anion.

Phonon dispersions, band structures, and dielectric functions of BeO and BeS polymorphs

NASA Astrophysics Data System (ADS)

Wang, Ke-Long; Gao, Shang-Peng

2018-07-01

Structures, phonon dispersions, electronic structures, and dielectric functions of beryllium oxide (BeO) and beryllium sulfide (BeS) polymorphs are investigated by density functional theory and many-body perturbation theory. Phonon calculations indicate that both wurtzite (w-) and zincblende (zb-) structures are dynamically stable for BeO and BeS, whereas rocksalt (rs-) structures for both BeO and BeS have imaginary phonon frequencies and thus are dynamically unstable at zero pressure. Band structures for the 4 dynamically stable phases show that only w-BeO has a direct band gap. Both the one-shot G0W0 and quasiparticle self-consistent GW methods are used to correct band energies at high symmetry k-points. Bethe-Salpeter equation (BSE), which considers Coulomb correlated electron-hole pairs, is employed to deal with the computation of macroscopic dielectric functions. It is shown that BSE calculation, employing scissors operator derived by self-consistent GW method, can give dielectric functions agreeing very well with experimental measurement of w-BeO. Weak anisotropic characters can be observed for w-BeO and w-BeS. Both zb-BeS and w-BeS show high optical transition probabilities within a narrow ultraviolet energy range.

Stochastic Optimally Tuned Range-Separated Hybrid Density Functional Theory.

PubMed

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.

The density-magnetic field relation in the atomic ISM

NASA Astrophysics Data System (ADS)

Gazol, A.; Villagran, M. A.

2018-07-01

We present numerical experiments aimed to study the correlation between the magnetic field strength, B, and the density, n, in the cold atomic interstellar medium (CNM). We analyse 24 magnetohydrodynamic models with different initial magnetic field intensities (B0 = 0.4, 2.1, 4.2, and 8.3 μG) and/or mean densities (2, 3, and 4 cm-3), in the presence of driven and decaying turbulence, with and without self-gravity, in a cubic computational domain with 100 pc by side. Our main findings are as follows: (i) For forced simulations that reproduce the main observed physical conditions of the CNM in the solar neighbourhood, a positive correlation between B and n develops for all the B0 values. (ii) The density at which this correlation becomes significant (≲30 cm-3) depends on B0 but is not sensitive to the presence of self-gravity. (iii) The effect of self-gravity, when noticeable, consists of producing a shallower correlation at high densities, suggesting that, in the studied regime, self-gravity induces motions along the field lines. (iv) Self-gravitating decaying models where the CNM is subsonic and sub-Alfvénic with β ≲ 1 develop a high-density positive correlation whose slopes are consistent with a constant β(n). (v) Decaying models where the low-density CNM is subsonic and sub-Alfvénic with β > 1 show a negative correlation at intermediate densities, followed by a high-density positive correlation.

The Density-Magnetic Field Relation in the Atomic ISM

NASA Astrophysics Data System (ADS)

Gazol, A.; Villagran, M. A.

2018-04-01

We present numerical experiments aimed to study the correlation between the magnetic field strength, B, and the density, n, in the cold atomic interstellar medium (CNM). We analyze 24 magneto-hydrodynamic models with different initial magnetic field intensities (B0 =0.4, 2.1, 4.2, and 8.3 μG) and/or mean densities (2, 3, and 4 cm-3), in the presence of driven and decaying turbulence, with and without self-gravity, in a cubic computational domain with 100 pc by side. Our main findings are: i) For forced simulations, which reproduce the main observed physical conditions of the CNM in the Solar neighborhood, a positive correlation between B and n develops for all the B0 values. ii) The density at which this correlation becomes significant (≲ 30 cm-3) depends on B0 but is not sensitive to the presence of self-gravity. iii) The effect of self-gravity, when noticeable, consists of producing a shallower correlation at high densities, suggesting that, in the studied regime, self-gravity induces motions along the field lines. iv) Self-gravitating decaying models where the CNM is subsonic and sub-Alfvénic with β ≲ 1 develop a high density positive correlation whose slopes are consistent with a constant β(n). v) Decaying models where the low density CNM is subsonic and sub-Alfvénic with β > 1 show a negative correlation at intermediate densities, followed by a high density positive correlation.

Opiates and cerebral functional activity in rats

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trusk, T.C.

1986-01-01

Cerebral activity was measured using the free-fatty acid (1-/sup 14/C) octanoate as a fast functional tracer in conscious, unrestrained rats 5 minutes after intravenous injection of heroin, cocaine or saline vehicle. Regional changes of octanoate labeling density in the autoradiograms relative to saline-injected animals were used to determine the functional activity effects of each drug. Heroin and cocaine each produced a distinctive pattern of activity increases and suppression throughout the rat brain. Similar regional changes induced by both drugs were found in limbic brain regions implicated in drug reinforcement. Labeled octanoate autoradiography was used to measure the cerebral functional responsemore » to a tone that had previously been paired to heroin injections. Rats were trained in groups of three consisting of one heroin self-administration animal, and two animals receiving yoked infusion of heroin or saline. A tone was paired with each infusion during training. Behavioral experiments in similarly trained rats demonstrated that these training conditions impart secondary reinforcing properties to the tone in animals previously self-administering heroin, while the tone remains behaviorally neutral in yoked-infusion rats. Cerebral functional activity was measured during presentation of the tone without drug infusion. Octanoate labeling density changed in fifteen brain areas in response to the tone previously paired to heroin without response contingency. Labeling density was significantly modified in sixteen regions as a result of previously pairing the tone to response-contingent heroin infusions.« less

Relativistic Coulomb Excitation within the Time Dependent Superfluid Local Density Approximation

NASA Astrophysics Data System (ADS)

Stetcu, I.; Bertulani, C. A.; Bulgac, A.; Magierski, P.; Roche, K. J.

2015-01-01

Within the framework of the unrestricted time-dependent density functional theory, we present for the first time an analysis of the relativistic Coulomb excitation of the heavy deformed open shell nucleus 238U. The approach is based on the superfluid local density approximation formulated on a spatial lattice that can take into account coupling to the continuum, enabling self-consistent studies of superfluid dynamics of any nuclear shape. We compute the energy deposited in the target nucleus as a function of the impact parameter, finding it to be significantly larger than the estimate using the Goldhaber-Teller model. The isovector giant dipole resonance, the dipole pygmy resonance, and giant quadrupole modes are excited during the process. The one-body dissipation of collective dipole modes is shown to lead a damping width Γ↓≈0.4 MeV and the number of preequilibrium neutrons emitted has been quantified.

Orbital relaxation effects on Kohn–Sham frontier orbital energies in density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, DaDi; Zheng, Xiao, E-mail: xz58@ustc.edu.cn; Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026

2015-04-21

We explore effects of orbital relaxation on Kohn–Sham frontier orbital energies in density functional theory by using a nonempirical scaling correction approach developed in Zheng et al. [J. Chem. Phys. 138, 174105 (2013)]. Relaxation of Kohn–Sham orbitals upon addition/removal of a fractional number of electrons to/from a finite system is determined by a systematic perturbative treatment. The information of orbital relaxation is then used to improve the accuracy of predicted Kohn–Sham frontier orbital energies by Hartree–Fock, local density approximation, and generalized gradient approximation methods. The results clearly highlight the significance of capturing the orbital relaxation effects. Moreover, the proposed scalingmore » correction approach provides a useful way of computing derivative gaps and Fukui quantities of N-electron finite systems (N is an integer), without the need to perform self-consistent-field calculations for (N ± 1)-electron systems.« less

Relativistic Coulomb excitation within the time dependent superfluid local density approximation

DOE PAGES

Stetcu, I.; Bertulani, C. A.; Bulgac, A.; ...

2015-01-06

Within the framework of the unrestricted time-dependent density functional theory, we present for the first time an analysis of the relativistic Coulomb excitation of the heavy deformed open shell nucleus 238U. The approach is based on the superfluid local density approximation formulated on a spatial lattice that can take into account coupling to the continuum, enabling self-consistent studies of superfluid dynamics of any nuclear shape. We compute the energy deposited in the target nucleus as a function of the impact parameter, finding it to be significantly larger than the estimate using the Goldhaber-Teller model. The isovector giant dipole resonance, themore » dipole pygmy resonance, and giant quadrupole modes are excited during the process. As a result, the one-body dissipation of collective dipole modes is shown to lead a damping width Γ↓≈0.4 MeV and the number of preequilibrium neutrons emitted has been quantified.« less

All-electron density functional calculation on insulin with quasi-canonical localized orbitals.

PubMed

Inaba, Toru; Tahara, Saisei; Nisikawa, Nobutaka; Kashiwagi, Hiroshi; Sato, Fumitoshi

2005-07-30

An all-electron density functional (DF) calculation on insulin was performed by the Gaussian-based DF program, ProteinDF. Quasi-canonical localized orbitals (QCLOs) were used to improve the initial guess for the self-consistent field (SCF) calculation. All calculations were carried out by parallel computing on eight processors of an Itanium2 cluster (SGI Altix3700) with a theoretical peak performance of 41.6 GFlops. It took 35 h for the whole calculation. Insulin is a protein hormone consisting of two peptide chains linked by three disulfide bonds. The numbers of residues, atoms, electrons, orbitals, and auxiliary functions are 51, 790, 3078, 4439, and 8060, respectively. An all-electron DF calculation on insulin was successfully carried out, starting from connected QCLOs. Regardless of a large molecule with complicated topology, the differences in the total energy and the Mulliken atomic charge between initial and converged wavefunctions were very small. The calculation proceeded smoothly without any trial and error, suggesting that this is a promising method to obtain SCF convergence on large molecules such as proteins.

Quantum Theory of Orbital Magnetization and Its Generalization to Interacting Systems

NASA Astrophysics Data System (ADS)

Shi, Junren; Vignale, G.; Xiao, Di; Niu, Qian

2007-11-01

Based on standard perturbation theory, we present a full quantum derivation of the formula for the orbital magnetization in periodic systems. The derivation is generally valid for insulators with or without a Chern number, for metals at zero or finite temperatures, and at weak as well as strong magnetic fields. The formula is shown to be valid in the presence of electron-electron interaction, provided the one-electron energies and wave functions are calculated self-consistently within the framework of the exact current and spin-density functional theory.

Quasi-Particle Self-Consistent GW for Molecules.

PubMed

Kaplan, F; Harding, M E; Seiler, C; Weigend, F; Evers, F; van Setten, M J

2016-06-14

We present the formalism and implementation of quasi-particle self-consistent GW (qsGW) and eigenvalue only quasi-particle self-consistent GW (evGW) adapted to standard quantum chemistry packages. Our implementation is benchmarked against high-level quantum chemistry computations (coupled-cluster theory) and experimental results using a representative set of molecules. Furthermore, we compare the qsGW approach for five molecules relevant for organic photovoltaics to self-consistent GW results (scGW) and analyze the effects of the self-consistency on the ground state density by comparing calculated dipole moments to their experimental values. We show that qsGW makes a significant improvement over conventional G0W0 and that partially self-consistent flavors (in particular evGW) can be excellent alternatives.

Theoretical study of triaxial shapes of neutron-rich Mo and Ru nuclei

DOE PAGES

Zhang, C. L.; Bhat, G. H.; Nazarewicz, W.; ...

2015-09-10

Here, whether atomic nuclei can possess triaxial shapes at their ground states is still a subject of ongoing debate. According to theory, good prospects for low-spin triaxiality are in the neutron-rich Mo-Ru region. Recently, transition quadrupole moments in rotational bands of even-mass neutron-rich isotopes of molybdenum and ruthenium nuclei have been measured. The new data have provided a challenge for theoretical descriptions invoking stable triaxial deformations. The purpose of this study is to understand experimental data on rotational bands in the neutron-rich Mo-Ru region, we carried out theoretical analysis of moments of inertia, shapes, and transition quadrupole moments of neutron-richmore » even-even nuclei around 110Ru using self-consistent mean-field and shell model techniques. Methods: To describe yrast structures in Mo and Ru isotopes, we use nuclear density functional theory (DFT) with the optimized energy density functional UNEDF0. We also apply triaxial projected shell model (TPSM) to describe yrast and positive-parity, near-yrast band structures. As a result, our self-consistent DFT calculations predict triaxial ground-state deformations in 106,108Mo and 108,110,112Ru and reproduce the observed low-frequency behavior of moments of inertia. As the rotational frequency increases, a negative-gamma structure, associated with the aligned ν(h 11/2) 2 pair, becomes energetically favored. The computed transition quadrupole moments vary with angular momentum, which reflects deformation changes with rotation; those variations are consistent with experiment. The TPSM calculations explain the observed band structures assuming stable triaxial shapes. Lastly, the structure of neutron-rich even-even nuclei around Ru-110 is consistent with triaxial shape deformations. Our DFT and TPSM frameworks provide a consistent and complementary description of experimental data.« less

Non-equilibrium STLS approach to transport properties of single impurity Anderson model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rezai, Raheleh, E-mail: R_Rezai@sbu.ac.ir; Ebrahimi, Farshad, E-mail: Ebrahimi@sbu.ac.ir

In this work, using the non-equilibrium Keldysh formalism, we study the effects of the electron–electron interaction and the electron-spin correlation on the non-equilibrium Kondo effect and the transport properties of the symmetric single impurity Anderson model (SIAM) at zero temperature by generalizing the self-consistent method of Singwi, Tosi, Land, and Sjolander (STLS) for a single-band tight-binding model with Hubbard type interaction to out of equilibrium steady-states. We at first determine in a self-consistent manner the non-equilibrium spin correlation function, the effective Hubbard interaction, and the double-occupancy at the impurity site. Then, using the non-equilibrium STLS spin polarization function in themore » non-equilibrium formalism of the iterative perturbation theory (IPT) of Yosida and Yamada, and Horvatic and Zlatic, we compute the spectral density, the current–voltage characteristics and the differential conductance as functions of the applied bias and the strength of on-site Hubbard interaction. We compare our spectral densities at zero bias with the results of numerical renormalization group (NRG) and depict the effects of the electron–electron interaction and electron-spin correlation at the impurity site on the aforementioned properties by comparing our numerical result with the order U{sup 2} IPT. Finally, we show that the obtained numerical results on the differential conductance have a quadratic universal scaling behavior and the resulting Kondo temperature shows an exponential behavior. -- Highlights: •We introduce for the first time the non-equilibrium method of STLS for Hubbard type models. •We determine the transport properties of SIAM using the non-equilibrium STLS method. •We compare our results with order-U2 IPT and NRG. •We show that non-equilibrium STLS, contrary to the GW and self-consistent RPA, produces the two Hubbard peaks in DOS. •We show that the method keeps the universal scaling behavior and correct exponential behavior of Kondo temperature.« less

Anharmonic frequencies of CX2Y2 (X, Y = O, N, F, H, D) isomers and related systems obtained from vibrational multiconfiguration self-consistent field theory.

PubMed

Pfeiffer, Florian; Rauhut, Guntram

2011-10-13

Accurate anharmonic frequencies are provided for molecules of current research, i.e., diazirines, diazomethane, the corresponding fluorinated and deuterated compounds, their dioxygen analogs, and others. Vibrational-state energies were obtained from state-specific vibrational multiconfiguration self-consistent field theory (VMCSCF) based on multilevel potential energy surfaces (PES) generated from explicitly correlated coupled cluster, CCSD(T)-F12a, and double-hybrid density functional calculations, B2PLYP. To accelerate the vibrational structure calculations, a configuration selection scheme as well as a polynomial representation of the PES have been exploited. Because experimental data are scarce for these systems, many calculated frequencies of this study are predictions and may guide experiments to come.

Self-consistent method for quantifying indium content from X-ray spectra of thick compound semiconductor specimens in a transmission electron microscope.

PubMed

Walther, T; Wang, X

2016-05-01

Based on Monte Carlo simulations of X-ray generation by fast electrons we calculate curves of effective sensitivity factors for analytical transmission electron microscopy based energy-dispersive X-ray spectroscopy including absorption and fluorescence effects, as a function of Ga K/L ratio for different indium and gallium containing compound semiconductors. For the case of InGaN alloy thin films we show that experimental spectra can thus be quantified without the need to measure specimen thickness or density, yielding self-consistent values for quantification with Ga K and Ga L lines. The effect of uncertainties in the detector efficiency are also shown to be reduced. © 2015 The Authors Journal of Microscopy © 2015 Royal Microscopical Society.

A density functional study on adsorption and dissociation of O 2 on Ir(1 0 0) surface

NASA Astrophysics Data System (ADS)

Erikat, I. A.; Hamad, B. A.; Khalifeh, J. M.

2011-06-01

The adsorption and the reaction barrier for the dissociation of O 2 on Ir(1 0 0) surface are studied using periodic self-consistent density functional theory (DFT) calculations. Dissociative adsorption is found to be energetically more favorable compared to molecular adsorption. Parallel approaches Prl1 and Prl2 on a hollow site with the same adsorption energy of -3.93 eV for both of them are found to have the most energetically preferred sites of adsorptions among all the studied cases. Hybridization between p-O 2 and d-metal orbitals is responsible for the dissociative adsorption. The minimum energy path is determined by using the nudge elastic band method (NEB). We found that the dissociation occurs immediately and very early in the dissociation path with a small activation barrier (0.26 eV), which means that molecular adsorption of O 2 on Ir(1 0 0) surface occurs at very low temperatures; this is consistent with previous experimental and theoretical studies on Ir surfaces.

A model study of tunneling conductance spectra of ferromagnetically ordered manganites

NASA Astrophysics Data System (ADS)

Panda, Saswati; Kar, J. K.; Rout, G. C.

2018-02-01

We report here the interplay of ferromagnetism (FM) and charge density wave (CDW) in manganese oxide systems through the study of tunneling conductance spectra. The model Hamiltonian consists of strong Heisenberg coupling in core t2g band electrons within mean-field approximation giving rise to ferromagnetism. Ferromagnetism is induced in the itinerant eg electrons due to Kubo-Ohata type double exchange (DE) interaction among the t2g and eg electrons. The charge ordering (CO) present in the eg band giving rise to CDW interaction is considered as the extra-mechanism to explain the colossal magnetoresistance (CMR) property of manganites. The magnetic and CDW order parameters are calculated using Zubarev's Green's function technique and solved self-consistently and numerically. The eg electron density of states (DOS) calculated from the imaginary part of the Green's function explains the experimentally observed tunneling conductance spectra. The DOS graph exhibits a parabolic gap near the Fermi energy as observed in tunneling conductance spectra experiments.

Finite amplitude method applied to the giant dipole resonance in heavy rare-earth nuclei

NASA Astrophysics Data System (ADS)

Oishi, Tomohiro; Kortelainen, Markus; Hinohara, Nobuo

2016-03-01

Background: The quasiparticle random phase approximation (QRPA), within the framework of nuclear density functional theory (DFT), has been a standard tool to access the collective excitations of atomic nuclei. Recently, the finite amplitude method (FAM) was developed in order to perform the QRPA calculations efficiently without any truncation on the two-quasiparticle model space. Purpose: We discuss the nuclear giant dipole resonance (GDR) in heavy rare-earth isotopes, for which the conventional matrix diagonalization of the QRPA is numerically demanding. A role of the Thomas-Reiche-Kuhn (TRK) sum rule enhancement factor, connected to the isovector effective mass, is also investigated. Methods: The electric dipole photoabsorption cross section was calculated within a parallelized FAM-QRPA scheme. We employed the Skyrme energy density functional self-consistently in the DFT calculation for the ground states and FAM-QRPA calculation for the excitations. Results: The mean GDR frequency and width are mostly reproduced with the FAM-QRPA, when compared to experimental data, although some deficiency is observed with isotopes heavier than erbium. A role of the TRK enhancement factor in actual GDR strength is clearly shown: its increment leads to a shift of the GDR strength to higher-energy region, without a significant change in the transition amplitudes. Conclusions: The newly developed FAM-QRPA scheme shows remarkable efficiency, which enables one to perform systematic analysis of GDR for heavy rare-earth nuclei. The theoretical deficiency of the photoabsorption cross section could not be improved by only adjusting the TRK enhancement factor, suggesting the necessity of an approach beyond self-consistent QRPA and/or a more systematic optimization of the energy density functional (EDF) parameters.

Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sundararaman, Ravishankar; Goddard, III, William A.; Arias, Tomas A.

First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solvemore » the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Lastly, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.« less

Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry.

PubMed

Sundararaman, Ravishankar; Goddard, William A; Arias, Tomas A

2017-03-21

First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solve the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Finally, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.

Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

DOE PAGES

Sundararaman, Ravishankar; Goddard, III, William A.; Arias, Tomas A.

2017-03-16

First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solvemore » the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Lastly, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.« less

Excited-state potential-energy surfaces of metal-adsorbed organic molecules from linear expansion Δ-self-consistent field density-functional theory (ΔSCF-DFT).

PubMed

Maurer, Reinhard J; Reuter, Karsten

2013-07-07

Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion Δ-self-consistent field method by Gavnholt et al. [Phys. Rev. B 78, 075441 (2008)] presents an efficient alternative to time consuming quasi-particle calculations. In this method, the standard Kohn-Sham equations of density-functional theory are solved with the constraint of a non-equilibrium occupation in a region of Hilbert-space resembling gas-phase orbitals of the adsorbate. In this work, we discuss the applicability of this method for the excited-state dynamics of metal-surface mounted organic adsorbates, specifically in the context of molecular switching. We present necessary advancements to allow for a consistent quality description of excited-state potential-energy surfaces (PESs), and illustrate the concept with the application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find that the explicit inclusion of substrate electronic states modifies the topologies of intra-molecular excited-state PESs of the molecule due to image charge and hybridization effects. While the molecule in gas phase shows a clear energetic separation of resonances that induce isomerization and backreaction, the surface-adsorbed molecule does not. The concomitant possibly simultaneous induction of both processes would lead to a significantly reduced switching efficiency of such a mechanism.

The unrestricted Hartree-Fock self consistent field calculation for spin density wave state in metallic carbon nanotube

NASA Astrophysics Data System (ADS)

Kobayashi, Katsushi

1997-06-01

The possibility of a spin density wave (SDW) state in a metallic carbon nanotube (CN) and its electronic properties are investigated within the Hartree-Fock self consistent field (SCF) energy-band calculation. Two kinds of spatial SDW states are assumed in this study. Each assumed SDW on the wave function is constructed with the degenerate π orbital in the metallic CN system. The results calculated for the one SDW model of CN always have a relative stability (˜ 0.1 eV/cell) in SCF total energy compared with the original model in which no SDW is assumed. All the results calculated for another SDW model are completely equal to the original one. Moreover, in the energy dispersion of the former stable SDW model, the degenerate π level found in the original model disappears and the band gap (3-5 eV) occurs around at the Fermi level. The energetic stability and the band gap are also found in the π-electron band calculation within the Hubbard Hamiltonian.

The impact of anisotropy and interaction range on the self-assembly of Janus ellipsoids

NASA Astrophysics Data System (ADS)

Ruth, D. P.; Gunton, J. D.; Rickman, J. M.; Li, Wei

2014-12-01

We assess the roles of anisotropy and interaction range on the self-assembly of Janus colloidal particles. In particular, Monte Carlo simulation is employed to investigate the propensity for the formation of aggregates in a spheroidal model of a colloid having a relatively short-ranged interaction that is consistent with experimentally realizable systems. By monitoring the equilibrium distribution of aggregates as a function of temperature and density, we identify a "micelle" transition temperature and discuss its dependence on particle shape. We find that, unlike systems with longer ranged interactions, this system does not form micelles below a transition temperature at low density. Rather, larger clusters comprising 20-40 particles characterize the transition. We then examine the dependence of the second virial coefficient on particle shape and well width to determine how these important system parameters affect aggregation. Finally, we discuss possible strategies suggested by this work to promote self-assembly for the encapsulation of particles.

Bulk dynamics of Brownian hard disks: Dynamical density functional theory versus experiments on two-dimensional colloidal hard spheres

NASA Astrophysics Data System (ADS)

Stopper, Daniel; Thorneywork, Alice L.; Dullens, Roel P. A.; Roth, Roland

2018-03-01

Using dynamical density functional theory (DDFT), we theoretically study Brownian self-diffusion and structural relaxation of hard disks and compare to experimental results on quasi two-dimensional colloidal hard spheres. To this end, we calculate the self-van Hove correlation function and distinct van Hove correlation function by extending a recently proposed DDFT-approach for three-dimensional systems to two dimensions. We find that the theoretical results for both self-part and distinct part of the van Hove function are in very good quantitative agreement with the experiments up to relatively high fluid packing fractions of roughly 0.60. However, at even higher densities, deviations between the experiment and the theoretical approach become clearly visible. Upon increasing packing fraction, in experiments, the short-time self-diffusive behavior is strongly affected by hydrodynamic effects and leads to a significant decrease in the respective mean-squared displacement. By contrast, and in accordance with previous simulation studies, the present DDFT, which neglects hydrodynamic effects, shows no dependence on the particle density for this quantity.

Nucleon localization and fragment formation in nuclear fission

DOE PAGES

Zhang, C. L.; Schuetrumpf, B.; Nazarewicz, W.

2016-12-27

An electron localization measure was originally introduced to characterize chemical bond structures in molecules. Recently, a nucleon localization based on Hartree-Fock densities has been introduced to investigate α-cluster structures in light nuclei. Compared to the local nucleonic densities, the nucleon localization function has been shown to be an excellent indicator of shell effects and cluster correlations. In this work, using the spatial nucleon localization measure, we investigated the emergence of fragments in fissioning heavy nuclei using the self-consistent energy density functional method with a quantified energy density functional optimized for fission studies. We studied the particle densities and spatial nucleonmore » localization distributions along the fission pathways of 264Fm, 232Th, and 240Pu. We demonstrated that the fission fragments were formed fairly early in the evolution, well before scission. To illustrate the usefulness of the localization measure, we showed how the hyperdeformed state of 232Th could be understood in terms of a quasimolecular state made of 132Sn and 100Zr fragments. Compared to nucleonic distributions, the nucleon localization function more effectively quantifies nucleonic clustering: its characteristic oscillating pattern, traced back to shell effects, is a clear fingerprint of cluster/fragment configurations. This is of particular interest for studies of fragment formation and fragment identification in fissioning nuclei.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, C. L.; Schuetrumpf, B.; Nazarewicz, W.

An electron localization measure was originally introduced to characterize chemical bond structures in molecules. Recently, a nucleon localization based on Hartree-Fock densities has been introduced to investigate α-cluster structures in light nuclei. Compared to the local nucleonic densities, the nucleon localization function has been shown to be an excellent indicator of shell effects and cluster correlations. In this work, using the spatial nucleon localization measure, we investigated the emergence of fragments in fissioning heavy nuclei using the self-consistent energy density functional method with a quantified energy density functional optimized for fission studies. We studied the particle densities and spatial nucleonmore » localization distributions along the fission pathways of 264Fm, 232Th, and 240Pu. We demonstrated that the fission fragments were formed fairly early in the evolution, well before scission. To illustrate the usefulness of the localization measure, we showed how the hyperdeformed state of 232Th could be understood in terms of a quasimolecular state made of 132Sn and 100Zr fragments. Compared to nucleonic distributions, the nucleon localization function more effectively quantifies nucleonic clustering: its characteristic oscillating pattern, traced back to shell effects, is a clear fingerprint of cluster/fragment configurations. This is of particular interest for studies of fragment formation and fragment identification in fissioning nuclei.« less

Form-function analysis of the effect of canopy morphology on leaf self-shading in the seagrass Thalassia testudinum.

PubMed

Enríquez, Susana; Pantoja-Reyes, Norma I

2005-09-01

The variation in seagrass morphology and the magnitude of leaf self-shading within the canopy of Thalassia testudinum, were compared among nine sites in a fringing reef lagoon. We found a significant variation in the growth-form of T. testudinum reflected in a 5.4-fold variation in the attenuation coefficient (K (d)) within the canopy. The largest morphological variation was observed in shoot density. Leaf biomass, leaf area index (LAI), and shoot density were positively associated with canopy-K (d) and with the percentage of surface irradiance received by the top of the seagrass canopy (% Es). These results provide an explanation for the consistent pattern of depth reduction in seagrass leaf biomass and shoot density reported in the literature. Shoot density and shoot size are two descriptors of the growth-form of T. testudinum related to its clonal life-form. Shoot size was not significantly correlated with canopy-K (d), nevertheless, it showed a significant effect on the slope of the relationship between shoot density and canopy-K (d). According to this model, shoot size also contributes to light attenuation within the seagrass canopy by increasing the effect of shoot density. This form-function analysis suggests that light may have a relevant role in the regulation of the optimal plant balance between horizontal (variation in shoot density) and vertical (variation in shoot size) growth of seagrasses. Other environmental factors and interactions also need to be examined to fully understand the mechanistic bases of the morphological responses of seagrasses to the environment.

Redox potential distribution of an organic-rich contaminated site obtained by the inversion of self-potential data

NASA Astrophysics Data System (ADS)

Abbas, M.; Jardani, A.; Soueid Ahmed, A.; Revil, A.; Brigaud, L.; Bégassat, Ph.; Dupont, J. P.

2017-11-01

Mapping the redox potential of shallow aquifers impacted by hydrocarbon contaminant plumes is important for the characterization and remediation of such contaminated sites. The redox potential of groundwater is indicative of the biodegradation of hydrocarbons and is important in delineating the shapes of contaminant plumes. The self-potential method was used to reconstruct the redox potential of groundwater associated with an organic-rich contaminant plume in northern France. The self-potential technique is a passive technique consisting in recording the electrical potential distribution at the surface of the Earth. A self-potential map is essentially the sum of two contributions, one associated with groundwater flow referred to as the electrokinetic component, and one associated with redox potential anomalies referred to as the electroredox component (thermoelectric and diffusion potentials are generally negligible). A groundwater flow model was first used to remove the electrokinetic component from the observed self-potential data. Then, a residual self-potential map was obtained. The source current density generating the residual self-potential signals is assumed to be associated with the position of the water table, an interface characterized by a change in both the electrical conductivity and the redox potential. The source current density was obtained through an inverse problem by minimizing a cost function including a data misfit contribution and a regularizer. This inversion algorithm allows the determination of the vertical and horizontal components of the source current density taking into account the electrical conductivity distribution of the saturated and non-saturated zones obtained independently by electrical resistivity tomography. The redox potential distribution was finally determined from the inverted residual source current density. A redox map was successfully built and the estimated redox potential values correlated well with in-situ measurements.

Self consistent solution of the tJ model in the overdoped regime

NASA Astrophysics Data System (ADS)

Shastry, B. Sriram; Hansen, Daniel

2013-03-01

Detailed results from a recent microscopic theory of extremely correlated Fermi liquids, applied to the t-J model in two dimensions, are presented. The theory is to second order in a parameter λ, and is valid in the overdoped regime of the tJ model. The solution reported here is from Ref, where relevant equations given in Ref are self consistently solved for the square lattice. Thermodynamic variables and the resistivity are displayed at various densities and T for two sets of band parameters. The momentum distribution function and the renormalized electronic dispersion, its width and asymmetry are reported along principal directions of the zone. The optical conductivity is calculated. The electronic spectral function A (k , ω) probed in ARPES, is detailed with different elastic scattering parameters to account for the distinction between LASER and synchrotron ARPES. A high (binding) energy waterfall feature, sensitively dependent on the band hopping parameter t' is noted. This work was supported by DOE under Grant No. FG02-06ER46319.

Communication: Hilbert-space partitioning of the molecular one-electron density matrix with orthogonal projectors

NASA Astrophysics Data System (ADS)

Vanfleteren, Diederik; Van Neck, Dimitri; Bultinck, Patrick; Ayers, Paul W.; Waroquier, Michel

2010-12-01

A double-atom partitioning of the molecular one-electron density matrix is used to describe atoms and bonds. All calculations are performed in Hilbert space. The concept of atomic weight functions (familiar from Hirshfeld analysis of the electron density) is extended to atomic weight matrices. These are constructed to be orthogonal projection operators on atomic subspaces, which has significant advantages in the interpretation of the bond contributions. In close analogy to the iterative Hirshfeld procedure, self-consistency is built in at the level of atomic charges and occupancies. The method is applied to a test set of about 67 molecules, representing various types of chemical binding. A close correlation is observed between the atomic charges and the Hirshfeld-I atomic charges.

Linear-scaling method for calculating nuclear magnetic resonance chemical shifts using gauge-including atomic orbitals within Hartree-Fock and density-functional theory.

PubMed

Kussmann, Jörg; Ochsenfeld, Christian

2007-08-07

Details of a new density matrix-based formulation for calculating nuclear magnetic resonance chemical shifts at both Hartree-Fock and density functional theory levels are presented. For systems with a nonvanishing highest occupied molecular orbital-lowest unoccupied molecular orbital gap, the method allows us to reduce the asymptotic scaling order of the computational effort from cubic to linear, so that molecular systems with 1000 and more atoms can be tackled with today's computers. The key feature is a reformulation of the coupled-perturbed self-consistent field (CPSCF) theory in terms of the one-particle density matrix (D-CPSCF), which avoids entirely the use of canonical MOs. By means of a direct solution for the required perturbed density matrices and the adaptation of linear-scaling integral contraction schemes, the overall scaling of the computational effort is reduced to linear. A particular focus of our formulation is to ensure numerical stability when sparse-algebra routines are used to obtain an overall linear-scaling behavior.

Approaching the basis set limit for DFT calculations using an environment-adapted minimal basis with perturbation theory: Formulation, proof of concept, and a pilot implementation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mao, Yuezhi; Horn, Paul R.; Mardirossian, Narbe

2016-07-28

Recently developed density functionals have good accuracy for both thermochemistry (TC) and non-covalent interactions (NC) if very large atomic orbital basis sets are used. To approach the basis set limit with potentially lower computational cost, a new self-consistent field (SCF) scheme is presented that employs minimal adaptive basis (MAB) functions. The MAB functions are optimized on each atomic site by minimizing a surrogate function. High accuracy is obtained by applying a perturbative correction (PC) to the MAB calculation, similar to dual basis approaches. Compared to exact SCF results, using this MAB-SCF (PC) approach with the same large target basis set producesmore » <0.15 kcal/mol root-mean-square deviations for most of the tested TC datasets, and <0.1 kcal/mol for most of the NC datasets. The performance of density functionals near the basis set limit can be even better reproduced. With further improvement to its implementation, MAB-SCF (PC) is a promising lower-cost substitute for conventional large-basis calculations as a method to approach the basis set limit of modern density functionals.« less

Communication: xDH double hybrid functionals can be qualitatively incorrect for non-equilibrium geometries: Dipole moment inversion and barriers to radical-radical association using XYG3 and XYGJ-OS

NASA Astrophysics Data System (ADS)

Hait, Diptarka; Head-Gordon, Martin

2018-05-01

Double hybrid (DH) density functionals are amongst the most accurate density functional approximations developed so far, largely due to the incorporation of correlation effects from unoccupied orbitals via second order perturbation theory (PT2). The xDH family of DH functionals calculate energy directly from orbitals optimized by a lower level approach like B3LYP, without self-consistent optimization. XYG3 and XYGJ-OS are two widely used xDH functionals that are known to be quite accurate at equilibrium geometries. Here, we show that the XYG3 and XYGJ-OS functionals can be ill behaved for stretched bonds well beyond the Coulson-Fischer point, predicting unphysical dipole moments and humps in potential energy curves for some simple systems like the hydrogen fluoride molecule. Numerical experiments and analysis show that these failures are not due to PT2. Instead, a large mismatch at stretched bond-lengths between the reference B3LYP orbitals and the optimized orbitals associated with the non-PT2 part of XYG3 leads to an unphysically large non-Hellman-Feynman contribution to first order properties like forces and electron densities.

Local Fitting of the Kohn-Sham Density in a Gaussian and Plane Waves Scheme for Large-Scale Density Functional Theory Simulations.

PubMed

Golze, Dorothea; Iannuzzi, Marcella; Hutter, Jürg

2017-05-09

A local resolution-of-the-identity (LRI) approach is introduced in combination with the Gaussian and plane waves (GPW) scheme to enable large-scale Kohn-Sham density functional theory calculations. In GPW, the computational bottleneck is typically the description of the total charge density on real-space grids. Introducing the LRI approximation, the linear scaling of the GPW approach with respect to system size is retained, while the prefactor for the grid operations is reduced. The density fitting is an O(N) scaling process implemented by approximating the atomic pair densities by an expansion in one-center fit functions. The computational cost for the grid-based operations becomes negligible in LRIGPW. The self-consistent field iteration is up to 30 times faster for periodic systems dependent on the symmetry of the simulation cell and on the density of grid points. However, due to the overhead introduced by the local density fitting, single point calculations and complete molecular dynamics steps, including the calculation of the forces, are effectively accelerated by up to a factor of ∼10. The accuracy of LRIGPW is assessed for different systems and properties, showing that total energies, reaction energies, intramolecular and intermolecular structure parameters are well reproduced. LRIGPW yields also high quality results for extended condensed phase systems such as liquid water, ice XV, and molecular crystals.

Evolution of single-particle structure and beta-decay near 78Ni

NASA Astrophysics Data System (ADS)

Borzov, I. N.

2012-12-01

The extended self-consistent beta-decay model has been applied for bet-decay rates and delayed neutron emission probabilities of spherical neutron-rich isotopes near the r-process paths. Unlike a popular global FRDM+RPA model, in our fully microscopic approach, the Gamow-Teller and first-forbidden decays are treated on the same footing. The model has been augmented by blocking of the odd particle in order to account for important ground-state spin-parity inversion effect which has been shown to exist in the region of the most neutron-rich doubly-magic nucleus 78Ni. Finally, a newly developed form of density functional DF3a has been employed which gives a better spin-orbit splitting due to the modified tensor components of the density functional.

Local spin density functional investigations of a manganite with perovskite-type derived structures

NASA Astrophysics Data System (ADS)

Matar, S. F.; Studer, F.; Siberchicot, B.; Subramanian, M. A.; Demazeau, G.; Etourneau, J.

1998-11-01

The electronic and magnetic structures of the perovskite CaMnO3 are self-consistently calculated assuming two crystal structures at the same formula unit volume within the local spin density functional theory and the augmented spherical wave (ASW) method. From the comparisons of energy differences between the different magnetic states the ground state configuration is an insulator with G-type ordering. This result together with the magnitudes of the magnetic moments are in agreement with experiment. The influence of mixing between Mn and O is found spin dependent from the analysis of the crystal orbital overlap population (COOP) which enable to describe the chemical bond. The calculations underline a feature of a half metallic ferromagnet which could be connected with the colossal magnetoresistance (CMR) property of related compounds.

Superconductivity in 2D and nearly 2D: A Conserving Description

NASA Astrophysics Data System (ADS)

Deisz, John; Hess, Daryl; Serene, Joe

1998-03-01

In a previous work,(J.J. Deisz, D.W. Hess, and J.W. Serene, Phys. Rev. Lett., to appear.) we used a 2D Hubbard model with an attractive interaction to explicitly show that a superconducting state in the fluctuation exchange approximation (FEA) could be detected from self-consistent calculations of the internal energy and free energy as a function of a threaded flux. The FEA is a conserving approximation beyond mean field theory that includes the exchange of Cooper pair, density, and spin fluctuations. Here, we present extensions of our previous calculations and show a phase diagram as a function of interaction strength and density. We discuss the nature of the FEA phase transition in 2D and focus on how it changes with increasing coupling between planes.

Modeling of diffusive plasmas in local thermodynamic equilibrium with integral constraints: application to mercury-free high pressure discharge lamp mixtures

NASA Astrophysics Data System (ADS)

Janssen, J. F. J.; Suijker, J. L. G.; Peerenboom, K. S. C.; van Dijk, J.

2017-03-01

The mercury free lamp model previously discussed in Gnybida et al (2014 J. Phys. D: Appl. Phys. 47 125201) did not account for self-consistent diffusion and only included two molecular transitions. In this paper we apply, for the first time, a self-consistent diffusion algorithm that features (1) species/mass conservation up to machine accuracy and (2) an arbitrary mix of integral (total mass) and local (cold spot) constraints on the composition. Another advantage of this model is that the total pressure of the gas is calculated self consistently. Therefore, the usage of a predetermined pressure is no longer required. Additionally, the number of association processes has been increased from 2 to 6. The population as a function of interatomic separation determines the spectrum of the emitted continuum radiation. Previously, this population was calculated using the limit of low densities. In this work an expression is used that removes this limitation. The result of these improvements is that the agreement between the simulated and measured spectra has improved considerably.

A simplified implementation of van der Waals density functionals for first-principles molecular dynamics applications

NASA Astrophysics Data System (ADS)

Wu, Jun; Gygi, François

2012-06-01

We present a simplified implementation of the non-local van der Waals correlation functional introduced by Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)] and reformulated by Román-Pérez et al. [Phys. Rev. Lett. 103, 096102 (2009)]. The proposed numerical approach removes the logarithmic singularity of the kernel function. Complete expressions of the self-consistent correlation potential and of the stress tensor are given. Combined with various choices of exchange functionals, five versions of van der Waals density functionals are implemented. Applications to the computation of the interaction energy of the benzene-water complex and to the computation of the equilibrium cell parameters of the benzene crystal are presented. As an example of crystal structure calculation involving a mixture of hydrogen bonding and dispersion interactions, we compute the equilibrium structure of two polymorphs of aspirin (2-acetoxybenzoic acid, C9H8O4) in the P21/c monoclinic structure.

Bond breaking and bond formation: how electron correlation is captured in many-body perturbation theory and density-functional theory.

PubMed

Caruso, Fabio; Rohr, Daniel R; Hellgren, Maria; Ren, Xinguo; Rinke, Patrick; Rubio, Angel; Scheffler, Matthias

2013-04-05

For the paradigmatic case of H(2) dissociation, we compare state-of-the-art many-body perturbation theory in the GW approximation and density-functional theory in the exact-exchange plus random-phase approximation (RPA) for the correlation energy. For an unbiased comparison and to prevent spurious starting point effects, both approaches are iterated to full self-consistency (i.e., sc-RPA and sc-GW). The exchange-correlation diagrams in both approaches are topologically identical, but in sc-RPA they are evaluated with noninteracting and in sc-GW with interacting Green functions. This has a profound consequence for the dissociation region, where sc-RPA is superior to sc-GW. We argue that for a given diagrammatic expansion, sc-RPA outperforms sc-GW when it comes to bond breaking. We attribute this to the difference in the correlation energy rather than the treatment of the kinetic energy.

Influence of defects on the absorption edge of InN thin films: The band gap value

NASA Astrophysics Data System (ADS)

Thakur, J. S.; Danylyuk, Y. V.; Haddad, D.; Naik, V. M.; Naik, R.; Auner, G. W.

2007-07-01

We investigate the optical-absorption spectra of InN thin films whose electron density varies from ˜1017tõ1021cm-3 . The low-density films are grown by molecular-beam-epitaxy deposition while highly degenerate films are grown by plasma-source molecular-beam epitaxy. The optical-absorption edge is found to increase from 0.61to1.90eV as the carrier density of the films is increased from low to high density. Since films are polycrystalline and contain various types of defects, we discuss the band gap values by studying the influence of electron degeneracy, electron-electron, electron-ionized impurities, and electron-LO-phonon interaction self-energies on the spectral absorption coefficients of these films. The quasiparticle self-energies of the valence and conduction bands are calculated using dielectric screening within the random-phase approximation. Using one-particle Green’s function analysis, we self-consistently determine the chemical potential for films by coupling equations for the chemical potential and the single-particle scattering rate calculated within the effective-mass approximation for the electron scatterings from ionized impurities and LO phonons. By subtracting the influence of self-energies and chemical potential from the optical-absorption edge energy, we estimate the intrinsic band gap values for the films. We also determine the variations in the calculated band gap values due to the variations in the electron effective mass and static dielectric constant. For the lowest-density film, the estimated band gap energy is ˜0.59eV , while for the highest-density film, it varies from ˜0.60tõ0.68eV depending on the values of electron effective mass and dielectric constant.

Temperature as a third dimension in column-density mapping of dusty astrophysical structures associated with star formation

NASA Astrophysics Data System (ADS)

Marsh, K. A.; Whitworth, A. P.; Lomax, O.

2015-12-01

We present point process mapping (PPMAP), a Bayesian procedure that uses images of dust continuum emission at multiple wavelengths to produce resolution-enhanced image cubes of differential column density as a function of dust temperature and position. PPMAP is based on the generic `point process formalism, whereby the system of interest (in this case, a dusty astrophysical structure such as a filament or pre-stellar core) is represented by a collection of points in a suitably defined state space. It can be applied to a variety of observational data, such as Herschel images, provided only that the image intensity is delivered by optically thin dust in thermal equilibrium. PPMAP takes full account of the instrumental point-spread functions and does not require all images to be degraded to the same resolution. We present the results of testing using simulated data for a pre-stellar core and a fractal turbulent cloud, and demonstrate its performance with real data from the Herschel infrared Galactic Plane Survey (Hi-GAL). Specifically, we analyse observations of a large filamentary structure in the CMa OB1 giant molecular cloud. Histograms of differential column density indicate that the warm material (T ≳ 13 K) is distributed lognormally, consistent with turbulence, but the column densities of the cooler material are distributed as a high-density tail, consistent with the effects of self-gravity. The results illustrate the potential of PPMAP to aid in distinguishing between different physical components along the line of sight in star-forming clouds, and aid the interpretation of the associated Probability distribution functions (PDFs) of column density.

Collisionless distribution function for the relativistic force-free Harris sheet

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stark, C. R.; Neukirch, T.

A self-consistent collisionless distribution function for the relativistic analogue of the force-free Harris sheet is presented. This distribution function is the relativistic generalization of the distribution function for the non-relativistic collisionless force-free Harris sheet recently found by Harrison and Neukirch [Phys. Rev. Lett. 102, 135003 (2009)], as it has the same dependence on the particle energy and canonical momenta. We present a detailed calculation which shows that the proposed distribution function generates the required current density profile (and thus magnetic field profile) in a frame of reference in which the electric potential vanishes identically. The connection between the parameters ofmore » the distribution function and the macroscopic parameters such as the current sheet thickness is discussed.« less

A Self-Consistent Model of the Interacting Ring Current Ions and Electromagnetic Ion Cyclotron Waves, Initial Results: Waves and Precipitating Fluxes

NASA Technical Reports Server (NTRS)

Khazanov, G. V.; Gamayunov, K. V.; Jordanova, V. K.; Krivorutsky, E. N.

2002-01-01

Initial results from a newly developed model of the interacting ring current ions and ion cyclotron waves are presented. The model is based on the system of two kinetic equations: one equation describes the ring current ion dynamics, and another equation describes wave evolution. The system gives a self-consistent description of the ring current ions and ion cyclotron waves in a quasilinear approach. These equations for the ion phase space distribution function and for the wave power spectral density were solved on aglobal magnetospheric scale undernonsteady state conditions during the 2-5 May 1998 storm. The structure and dynamics of the ring current proton precipitating flux regions and the ion cyclotron wave-active zones during extreme geomagnetic disturbances on 4 May 1998 are presented and discussed in detail.

Cardiac Muscle-cell Based Actuator and Self-stabilizing Biorobot - PART 1.

PubMed

Holley, Merrel T; Nagarajan, Neerajha; Danielson, Christian; Zorlutuna, Pinar; Park, Kidong

2017-07-11

Biological machines often referred to as biorobots, are living cell- or tissue-based devices that are powered solely by the contractile activity of living components. Due to their inherent advantages, biorobots are gaining interest as alternatives to traditional fully artificial robots. Various studies have focused on harnessing the power of biological actuators, but only recently studies have quantitatively characterized the performance of biorobots and studied their geometry to enhance functionality and efficiency. Here, we demonstrate the development of a self-stabilizing swimming biorobot that can maintain its pitch, depth, and roll without external intervention. The design and fabrication of the PDMS scaffold for the biological actuator and biorobot followed by the functionalization with fibronectin is described in this first part. In the second part of this two-part article, we detail the incorporation of cardiomyocytes and characterize the biological actuator and biorobot function. Both incorporate a base and tail (cantilever) which produce fin-based propulsion. The tail is constructed with soft lithography techniques using PDMS and laser engraving. After incorporating the tail with the device base, it is functionalized with a cell adhesive protein and seeded confluently with cardiomyocytes. The base of the biological actuator consists of a solid PDMS block with a central glass bead (acts as a weight). The base of the biorobot consists of two composite PDMS materials, Ni-PDMS and microballoon-PDMS (MB-PDMS). The nickel powder (in Ni-PDMS) allows magnetic control of the biorobot during cells seeding and stability during locomotion. Microballoons (in MB-PDMS) decrease the density of MB-PDMS, and enable the biorobot to float and swim steadily. The use of these two materials with different mass densities, enabled precise control over the weight distribution to ensure a positive restoration force at any angle of the biorobot. This technique produces a magnetically controlled self-stabilizing swimming biorobot.

Nonadiabatic Dynamics for Electrons at Second-Order: Real-Time TDDFT and OSCF2.

PubMed

Nguyen, Triet S; Parkhill, John

2015-07-14

We develop a new model to simulate nonradiative relaxation and dephasing by combining real-time Hartree-Fock and density functional theory (DFT) with our recent open-systems theory of electronic dynamics. The approach has some key advantages: it has been systematically derived and properly relaxes noninteracting electrons to a Fermi-Dirac distribution. This paper combines the new dissipation theory with an atomistic, all-electron quantum chemistry code and an atom-centered model of the thermal environment. The environment is represented nonempirically and is dependent on molecular structure in a nonlocal way. A production quality, O(N(3)) closed-shell implementation of our theory applicable to realistic molecular systems is presented, including timing information. This scaling implies that the added cost of our nonadiabatic relaxation model, time-dependent open self-consistent field at second order (OSCF2), is computationally inexpensive, relative to adiabatic propagation of real-time time-dependent Hartree-Fock (TDHF) or time-dependent density functional theory (TDDFT). Details of the implementation and numerical algorithm, including factorization and efficiency, are discussed. We demonstrate that OSCF2 approaches the stationary self-consistent field (SCF) ground state when the gap is large relative to k(b)T. The code is used to calculate linear-response spectra including the effects of bath dynamics. Finally, we show how our theory of finite-temperature relaxation can be used to correct ground-state DFT calculations.

Equilibrium properties of simple metal thin films in the self-compressed stabilized jellium model.

PubMed

Mahmoodi, T; Payami, M

2009-07-01

In this work, we have applied the self-compressed stabilized jellium model to predict the equilibrium properties of isolated thin Al, Na and Cs slabs. To make a direct correspondence to atomic slabs, we have considered only those L values that correspond to n-layered atomic slabs with 2≤n≤20, for surface indices (100), (110), and (111). The calculations are based on the density functional theory and self-consistent solution of the Kohn-Sham equations in the local density approximation. Our results show that firstly, the quantum size effects are significant for slabs with sizes smaller than or near to the Fermi wavelength of the valence electrons λ(F), and secondly, some slabs expand while others contract with respect to the bulk spacings. Based on the results, we propose a criterion for realization of significant quantum size effects that lead to expansion of some thin slabs. For more justification of the criterion, we have tested it on Li slabs for 2≤n≤6. We have compared our Al results with those obtained from using all-electron or pseudo-potential first-principles calculations. This comparison shows excellent agreements for Al(100) work functions, and qualitatively good agreements for the other work functions and surface energies. These agreements justify the way we have used the self-compressed stabilized jellium model for the correct description of the properties of simple metal slab systems. On the other hand, our results for the work functions and surface energies of large- n slabs are in good agreement with those obtained from applying the stabilized jellium model for semi-infinite systems. In addition, we have performed the slab calculations in the presence of surface corrugation for selected Al slabs and have shown that the results are worsened.

Psi4 1.1: An Open-Source Electronic Structure Program Emphasizing Automation, Advanced Libraries, and Interoperability.

PubMed

Parrish, Robert M; Burns, Lori A; Smith, Daniel G A; Simmonett, Andrew C; DePrince, A Eugene; Hohenstein, Edward G; Bozkaya, Uğur; Sokolov, Alexander Yu; Di Remigio, Roberto; Richard, Ryan M; Gonthier, Jérôme F; James, Andrew M; McAlexander, Harley R; Kumar, Ashutosh; Saitow, Masaaki; Wang, Xiao; Pritchard, Benjamin P; Verma, Prakash; Schaefer, Henry F; Patkowski, Konrad; King, Rollin A; Valeev, Edward F; Evangelista, Francesco A; Turney, Justin M; Crawford, T Daniel; Sherrill, C David

2017-07-11

Psi4 is an ab initio electronic structure program providing methods such as Hartree-Fock, density functional theory, configuration interaction, and coupled-cluster theory. The 1.1 release represents a major update meant to automate complex tasks, such as geometry optimization using complete-basis-set extrapolation or focal-point methods. Conversion of the top-level code to a Python module means that Psi4 can now be used in complex workflows alongside other Python tools. Several new features have been added with the aid of libraries providing easy access to techniques such as density fitting, Cholesky decomposition, and Laplace denominators. The build system has been completely rewritten to simplify interoperability with independent, reusable software components for quantum chemistry. Finally, a wide range of new theoretical methods and analyses have been added to the code base, including functional-group and open-shell symmetry adapted perturbation theory, density-fitted coupled cluster with frozen natural orbitals, orbital-optimized perturbation and coupled-cluster methods (e.g., OO-MP2 and OO-LCCD), density-fitted multiconfigurational self-consistent field, density cumulant functional theory, algebraic-diagrammatic construction excited states, improvements to the geometry optimizer, and the "X2C" approach to relativistic corrections, among many other improvements.

Synthesis, characterization and calculated non-linear optical properties of two new chalcones

NASA Astrophysics Data System (ADS)

Singh, Ashok Kumar; Saxena, Gunjan; Prasad, Rajendra; Kumar, Abhinav

2012-06-01

Two new chalcones viz 3-(4-(benzyloxy)phenyl)-1-(2-hydroxyphenyl)prop-2-en-1-one (1) and 3-(4-chlorophenyl)-1-(2-hydroxyphenyl)prop-2-en-1-one (2) have been prepared and characterized by micro analyses, 1H NMR, IR, UV-Vis spectroscopy and single crystal X-ray. The first static hyperpolarizability (β) for both the compounds has been investigated by density functional theory (DFT). Also, the solvent-induced effects on the non-linear optical properties (NLO) were studied by using self-consistent reaction field (SCRF) method. As the solvent polarity increases, the β value increases monotonically. The electronic absorption bands of both 1 and 2 have been assigned by time dependent density functional theory (TD-DFT). Both the compounds displayed better non-linear optical (NLO) responses than the standard p-nitroaniline (pNA).

A third-generation density-functional-theory-based method for calculating canonical molecular orbitals of large molecules.

PubMed

Hirano, Toshiyuki; Sato, Fumitoshi

2014-07-28

We used grid-free modified Cholesky decomposition (CD) to develop a density-functional-theory (DFT)-based method for calculating the canonical molecular orbitals (CMOs) of large molecules. Our method can be used to calculate standard CMOs, analytically compute exchange-correlation terms, and maximise the capacity of next-generation supercomputers. Cholesky vectors were first analytically downscaled using low-rank pivoted CD and CD with adaptive metric (CDAM). The obtained Cholesky vectors were distributed and stored on each computer node in a parallel computer, and the Coulomb, Fock exchange, and pure exchange-correlation terms were calculated by multiplying the Cholesky vectors without evaluating molecular integrals in self-consistent field iterations. Our method enables DFT and massively distributed memory parallel computers to be used in order to very efficiently calculate the CMOs of large molecules.

Many-body perturbation theory using the density-functional concept: beyond the GW approximation.

PubMed

Bruneval, Fabien; Sottile, Francesco; Olevano, Valerio; Del Sole, Rodolfo; Reining, Lucia

2005-05-13

We propose an alternative formulation of many-body perturbation theory that uses the density-functional concept. Instead of the usual four-point integral equation for the polarizability, we obtain a two-point one, which leads to excellent optical absorption and energy-loss spectra. The corresponding three-point vertex function and self-energy are then simply calculated via an integration, for any level of approximation. Moreover, we show the direct impact of this formulation on the time-dependent density-functional theory. Numerical results for the band gap of bulk silicon and solid argon illustrate corrections beyond the GW approximation for the self-energy.

Electric dipole moment of diatomic molecules by configuration interaction. V - Two states of /2/Sigma/+/ symmetry in CN.

NASA Technical Reports Server (NTRS)

Green, S.

1972-01-01

Previous accurate dipole moment calculation techniques are modified to be applicable to higher excited states of symmetry. The self-consistent fields and configuration interactions are calculated for the X(2)Sigma(+) and B(2)Sigma(+) states of CN. Spin hyperfine constants and spin density at the nucleus are considered in the context of one-electron operator properties. The values of the self-consistent field and configuration interaction for the spin density are compared with experimental values for several diatomic molecules.

The tight binding model study of the role of anisotropic AFM spin ordering in the charge ordered CMR manganites

NASA Astrophysics Data System (ADS)

Kar, J. K.; Panda, Saswati; Rout, G. C.

2017-05-01

We propose here a tight binding model study of the interplay between charge and spin orderings in the CMR manganites taking anisotropic effect due to electron hoppings and spin exchanges. The Hamiltonian consists of the kinetic energies of eg and t2g electrons of manganese ion. It further includes double exchange and Heisenberg interactions. The charge density wave interaction (CDW) describes an extra mechanism for the insulating character of the system. The CDW gap and spin parameters are calculated using Zubarev's Green's function technique and computed self-consistently. The results are reported in this communication.

Electron correlation and the self-interaction error of density functional theory

NASA Astrophysics Data System (ADS)

Polo, Victor; Kraka, Elfi; Cremer, Dieter

The self-interaction error (SIE) of commonly used DFT functionals has been systematically investigated by comparing the electron density distribution ρ( r ) generated by self-interaction corrected DFT (SIC-DFT) with a series of reference densities obtained by DFT or wavefunction theory (WFT) methods that cover typical electron correlation effects. Although the SIE of GGA functionals is considerably smaller than that of LDA functionals, it has significant consequences for the coverage of electron correlation effects at the DFT level of theory. The exchange SIE mimics long range (non-dynamic) pair correlation effects, and is responsible for the fact that the electron density of DFT exchange-only calculations resembles often that of MP4, MP2 or even CCSD(T) calculations. Changes in the electron density caused by SICDFT exchange are comparable with those that are associated with HF exchange. Correlation functionals contract the density towards the bond and the valence region, thus taking negative charge out of the van der Waals region where these effects are exaggerated by the influence of the SIE of the correlation functional. Hence, SIC-DFT leads in total to a relatively strong redistribution of negative charge from van der Waals, non-bonding, and valence regions of heavy atoms to the bond regions. These changes, although much stronger, resemble those obtained when comparing the densities of hybrid functionals such as B3LYP with the corresponding GGA functional BLYP. Hence, the balanced mixing of local and non-local exchange and correlation effects as it is achieved by hybrid functionals mimics SIC-DFT and can be considered as an economic way to include some SIC into standard DFT. However, the investigation shows also that the SIC-DFT description of molecules is unreliable because the standard functionals used were optimized for DFT including the SIE.

An environment-dependent semi-empirical tight binding model suitable for electron transport in bulk metals, metal alloys, metallic interfaces, and metallic nanostructures. I. Model and validation

NASA Astrophysics Data System (ADS)

Hegde, Ganesh; Povolotskyi, Michael; Kubis, Tillmann; Boykin, Timothy; Klimeck, Gerhard

2014-03-01

Semi-empirical Tight Binding (TB) is known to be a scalable and accurate atomistic representation for electron transport for realistically extended nano-scaled semiconductor devices that might contain millions of atoms. In this paper, an environment-aware and transferable TB model suitable for electronic structure and transport simulations in technologically relevant metals, metallic alloys, metal nanostructures, and metallic interface systems are described. Part I of this paper describes the development and validation of the new TB model. The new model incorporates intra-atomic diagonal and off-diagonal elements for implicit self-consistency and greater transferability across bonding environments. The dependence of the on-site energies on strain has been obtained by appealing to the Moments Theorem that links closed electron paths in the system to energy moments of angular momentum resolved local density of states obtained ab initio. The model matches self-consistent density functional theory electronic structure results for bulk face centered cubic metals with and without strain, metallic alloys, metallic interfaces, and metallic nanostructures with high accuracy and can be used in predictive electronic structure and transport problems in metallic systems at realistically extended length scales.

On the subsystem formulation of linear-response time-dependent DFT.

PubMed

Pavanello, Michele

2013-05-28

A new and thorough derivation of linear-response subsystem time-dependent density functional theory (TD-DFT) is presented and analyzed in detail. Two equivalent derivations are presented and naturally yield self-consistent subsystem TD-DFT equations. One reduces to the subsystem TD-DFT formalism of Neugebauer [J. Chem. Phys. 126, 134116 (2007)]. The other yields Dyson type equations involving three types of subsystem response functions: coupled, uncoupled, and Kohn-Sham. The Dyson type equations for subsystem TD-DFT are derived here for the first time. The response function formalism reveals previously hidden qualities and complications of subsystem TD-DFT compared with the regular TD-DFT of the supersystem. For example, analysis of the pole structure of the subsystem response functions shows that each function contains information about the electronic spectrum of the entire supersystem. In addition, comparison of the subsystem and supersystem response functions shows that, while the correlated response is subsystem additive, the Kohn-Sham response is not. Comparison with the non-subjective partition DFT theory shows that this non-additivity is largely an artifact introduced by the subjective nature of the density partitioning in subsystem DFT.

Effective charges of ionic liquid determined self-consistently through combination of molecular dynamics simulation and density-functional theory.

PubMed

Ishizuka, Ryosuke; Matubayasi, Nobuyuki

2017-11-15

A self-consistent scheme combining the molecular dynamics (MD) simulation and density functional theory (DFT) was recently proposed to incorporate the effects of the charge transfer and polarization of ions into non-poralizable force fields of ionic liquids for improved description of energetics and dynamics. The purpose of the present work is to analyze the detailed setups of the MD/DFT scheme by focusing on how the basis set, exchange-correlation (XC) functional, charge-fitting method or force field for the intramolecular and Lennard-Jones interactions affects the MD/DFT results of 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl) imide ( [C1mim][NTf2]) and 1-ethyl-3-methylimidazolium glycinate ( [C2mim][Gly]). It was found that the double-zeta valence polarized or larger size of basis set is required for the convergence of the effective charge of the ion. The choice of the XC functional was further not influential as far as the generalized gradient approximation is used. The charge-fitting method and force field govern the accuracy of the MD/DFT scheme, on the other hand. We examined the charge-fitting methods of Blöchl, the iterative Hirshfeld (Hirshfeld-I), and REPEAT in combination with Lopes et al.'s force field and general AMBER force field. There is no single combination of charge fitting and force field that provides good agreements with the experiments, while the MD/DFT scheme reduces the effective charges of the ions and leads to better description of energetics and dynamics compared to the original force field with unit charges. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

A non-JKL density matrix functional for intergeminal correlation between closed-shell geminals from analysis of natural orbital configuration interaction expansions

NASA Astrophysics Data System (ADS)

van Meer, R.; Gritsenko, O. V.; Baerends, E. J.

2018-03-01

Almost all functionals that are currently used in density matrix functional theory have been created by some a priori ansatz that generates approximations to the second-order reduced density matrix (2RDM). In this paper, a more consistent approach is used: we analyze the 2RDMs (in the natural orbital basis) of rather accurate multi-reference configuration interaction expansions for several small molecules (CH4, NH3, H2O, FH, and N2) and use the knowledge gained to generate new functionals. The analysis shows that a geminal-like structure is present in the 2RDMs, even though no geminal theory has been applied from the onset. It is also shown that the leading non-geminal dynamical correlation contributions are generated by a specific set of double excitations. The corresponding determinants give rise to non-JKL (non Coulomb/Exchange like) multipole-multipole dispersive attractive terms between geminals. Due to the proximity of the geminals, these dispersion terms are large and cannot be omitted, proving pure JKL functionals to be essentially deficient. A second correction emerges from the observation that the "normal" geminal-like exchange between geminals breaks down when one breaks multiple bonds. This problem can be fixed by doubling the exchange between bond broken geminals, effectively restoring the often physically correct high-spin configurations on the bond broken fragments. Both of these corrections have been added to the commonly used antisymmetrized product of strongly orthogonal geminals functional. The resulting non-JKL functional Extended Löwdin-Shull Dynamical-Multibond is capable of reproducing complete active space self-consistent field curves, in which one active orbital is used for each valence electron.

Ground State Structure Search of Fluoroperovskites through Lattice Instability

NASA Astrophysics Data System (ADS)

Mei, W. N.; Hatch, D. M.; Stokes, H. T.; Boyer, L. L.

2002-03-01

Many Fluoroperovskite are capable of a ferroelectric transition from a cubic to a tetragonal and even lower-symmetry structures. In this work, we studied systematically the structural phase transitions of several fluoroperovskites ABF3 where A= Na, K and B= Ca, Sr. Combining the Self-Consistent Atom Deformation (SCAD) -- a density-functional method using localized densities -- and the frozen-phonon method which utilizes the isotropy subgroup operations, we calculate the phonon energies and find instabilities which lower the symmetry of the crystal. Following this scheme, we work down to lower symmetry structures until we no longer find instabilities. The final results are used to compare with those obtained from molecular dynamics based on Gordon-Kim potentials.

Rough Interface Effects on N-S Proximity-Contact Systems

NASA Astrophysics Data System (ADS)

Nagato, Yasushi; Nagai, Katsuhiko

2003-03-01

We discuss the influence of atomic scale roughness of the interface on the properties of the N-S contact systems. To treat the interface roughness effects we extend our previous quasi-classical theory of the rough surface effect and construct a formal solution for the quasi-classical Green's function. We apply the formulation to N-S systems with two-dimensional anisotropic dx2-y2 superconductor and calculate the self-consistent pair potential and the density of states at the interface.

Renormalized dynamics of the Dean-Kawasaki model

NASA Astrophysics Data System (ADS)

Bidhoodi, Neeta; Das, Shankar P.

2015-07-01

We study the model of a supercooled liquid for which the equation of motion for the coarse-grained density ρ (x ,t ) is the nonlinear diffusion equation originally proposed by Dean and Kawasaki, respectively, for Brownian and Newtonian dynamics of fluid particles. Using a Martin-Siggia-Rose (MSR) field theory we study the renormalization of the dynamics in a self-consistent form in terms of the so-called self-energy matrix Σ . The appropriate model for the renormalized dynamics involves an extended set of field variables {ρ ,θ } , linked through a nonlinear constraint. The latter incorporates, in a nonperturbative manner, the effects of an infinite number of density nonlinearities in the dynamics. We show that the contributing element of Σ which renormalizes the bare diffusion constant D0 to DR is same as that proposed by Kawasaki and Miyazima [Z. Phys. B Condens. Matter 103, 423 (1997), 10.1007/s002570050396]. DR sharply decreases with increasing density. We consider the likelihood of a ergodic-nonergodic (ENE) transition in the model beyond a critical point. The transition is characterized by the long-time limit of the density correlation freezing at a nonzero value. From our analysis we identify an element of Σ which arises from the above-mentioned nonlinear constraint and is key to the viability of the ENE transition. If this self-energy would be zero, then the model supports a sharp ENE transition with DR=0 as predicted by Kawasaki and Miyazima. With the full model having nonzero value for this self-energy, the density autocorrelation function decays to zero in the long-time limit. Hence the ENE transition is not supported in the model.

Self-consistent continuum solvation for optical absorption of complex molecular systems in solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Timrov, Iurii; Biancardi, Alessandro; Andreussi, Oliviero

2015-01-21

We introduce a new method to compute the optical absorption spectra of complex molecular systems in solution, based on the Liouville approach to time-dependent density-functional perturbation theory and the revised self-consistent continuum solvation model. The former allows one to obtain the absorption spectrum over a whole wide frequency range, using a recently proposed Lanczos-based technique, or selected excitation energies, using the Casida equation, without having to ever compute any unoccupied molecular orbitals. The latter is conceptually similar to the polarizable continuum model and offers the further advantages of allowing an easy computation of atomic forces via the Hellmann-Feynman theorem andmore » a ready implementation in periodic-boundary conditions. The new method has been implemented using pseudopotentials and plane-wave basis sets, benchmarked against polarizable continuum model calculations on 4-aminophthalimide, alizarin, and cyanin and made available through the QUANTUM ESPRESSO distribution of open-source codes.« less

Comparison of several classical density functional theories for the adsorption of flexible chain molecules into cylindrical nanopores.

PubMed

Hlushak, S P; Cummings, P T; McCabe, C

2013-12-21

Adsorption of flexible oligomers into narrow cylindrical pores has been studied by means of several versions of classical density functional theory (CDFT) and Monte Carlo simulation. The adsorption process is interesting to study due to the competition between the entropic depletion of oligomers from the pores and the wall-oligomer attraction. It is also challenging to describe using current CDFTs, which tend to overestimate the amount of the adsorbed fluid. From a comparison of several different CDFT approaches, we find that this is due to the assumption of ideal or freely jointed chain conformations. Moreover, it is demonstrated that it is impossible to obtain a reasonable description of the adsorption isotherms without taking into account accurate contact values in the distribution functions describing the structure of the reference monomer fluid. At low densities, more accurate result are obtained in comparison with Monte Carlo simulation data when accurate contact values are incorporated into the theory rather than the more commonly used hard-sphere contact value. However, even the CDFT with accurate contact values still overestimates the amount of the adsorbed fluid due to the ideal or freely jointed chain approximation, used for the description of chain conformations in most CDFT approaches. We find that significant improvement can achieved by employing self-consistent field theory, which samples self-avoiding chain conformations and decreases the number of possible chain conformations, and, consequently, the amount of the adsorbed fluid.

Maximally localized Wannier functions in LaMnO3 within PBE + U, hybrid functionals and partially self-consistent GW: an efficient route to construct ab initio tight-binding parameters for eg perovskites.

PubMed

Franchini, C; Kováčik, R; Marsman, M; Murthy, S Sathyanarayana; He, J; Ederer, C; Kresse, G

2012-06-13

Using the newly developed VASP2WANNIER90 interface we have constructed maximally localized Wannier functions (MLWFs) for the e(g) states of the prototypical Jahn-Teller magnetic perovskite LaMnO(3) at different levels of approximation for the exchange-correlation kernel. These include conventional density functional theory (DFT) with and without the additional on-site Hubbard U term, hybrid DFT and partially self-consistent GW. By suitably mapping the MLWFs onto an effective e(g) tight-binding (TB) Hamiltonian we have computed a complete set of TB parameters which should serve as guidance for more elaborate treatments of correlation effects in effective Hamiltonian-based approaches. The method-dependent changes of the calculated TB parameters and their interplay with the electron-electron (el-el) interaction term are discussed and interpreted. We discuss two alternative model parameterizations: one in which the effects of the el-el interaction are implicitly incorporated in the otherwise 'noninteracting' TB parameters and a second where we include an explicit mean-field el-el interaction term in the TB Hamiltonian. Both models yield a set of tabulated TB parameters which provide the band dispersion in excellent agreement with the underlying ab initio and MLWF bands.

Estimating loblolly pine size-density trajectories across a range of planting densities

Treesearch

Curtis L. VanderSchaaf; Harold E. Burkhart

2013-01-01

Size-density trajectories on the logarithmic (ln) scale are generally thought to consist of two major stages. The first is often referred to as the density-independent mortality stage where the probability of mortality is independent of stand density; in the second, often referred to as the density-dependent mortality or self-thinning stage, the probability of...

Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pederson, Mark R., E-mail: mark.pederson@science.doe.gov

2015-02-14

A recent modification of the Perdew-Zunger self-interaction-correction to the density-functional formalism has provided a framework for explicitly restoring unitary invariance to the expression for the total energy. The formalism depends upon construction of Löwdin orthonormalized Fermi-orbitals which parametrically depend on variational quasi-classical electronic positions. Derivatives of these quasi-classical electronic positions, required for efficient minimization of the self-interaction corrected energy, are derived and tested, here, on atoms. Total energies and ionization energies in closed-shell singlet atoms, where correlation is less important, using the Perdew-Wang 1992 Local Density Approximation (PW92) functional, are in good agreement with experiment and non-relativistic quantum-Monte-Carlo results albeitmore » slightly too low.« less

STAR FORMATION IN TURBULENT MOLECULAR CLOUDS WITH COLLIDING FLOW

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsumoto, Tomoaki; Dobashi, Kazuhito; Shimoikura, Tomomi, E-mail: matsu@hosei.ac.jp

2015-03-10

Using self-gravitational hydrodynamical numerical simulations, we investigated the evolution of high-density turbulent molecular clouds swept by a colliding flow. The interaction of shock waves due to turbulence produces networks of thin filamentary clouds with a sub-parsec width. The colliding flow accumulates the filamentary clouds into a sheet cloud and promotes active star formation for initially high-density clouds. Clouds with a colliding flow exhibit a finer filamentary network than clouds without a colliding flow. The probability distribution functions (PDFs) for the density and column density can be fitted by lognormal functions for clouds without colliding flow. When the initial turbulence ismore » weak, the column density PDF has a power-law wing at high column densities. The colliding flow considerably deforms the PDF, such that the PDF exhibits a double peak. The stellar mass distributions reproduced here are consistent with the classical initial mass function with a power-law index of –1.35 when the initial clouds have a high density. The distribution of stellar velocities agrees with the gas velocity distribution, which can be fitted by Gaussian functions for clouds without colliding flow. For clouds with colliding flow, the velocity dispersion of gas tends to be larger than the stellar velocity dispersion. The signatures of colliding flows and turbulence appear in channel maps reconstructed from the simulation data. Clouds without colliding flow exhibit a cloud-scale velocity shear due to the turbulence. In contrast, clouds with colliding flow show a prominent anti-correlated distribution of thin filaments between the different velocity channels, suggesting collisions between the filamentary clouds.« less

Performance and Self-Consistency of the Generalized Dielectric Dependent Hybrid Functional

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brawand, Nicholas P.; Govoni, Marco; Vörös, Márton

Here, we analyze the performance of the recently proposed screened exchange constant functional (SX) on the GW100 test set, and we discuss results obtained at different levels of self-consistency. The SX functional is a generalization of dielectric dependent hybrid functionals to finite systems; it is nonempirical and depends on the average screening of the exchange interaction. We compare results for ionization potentials obtained with SX to those of CCSD(T) calculations and experiments, and we find excellent agreement, on par with recent state of the art methods based on many body perturbation theory. Applying SX perturbatively to correct PBE eigenvalues yieldsmore » improved results in most cases, except for ionic molecules, for which wave function self-consistency is instead crucial. Calculations where wave functions and the screened exchange constant (α SX) are determined self-consistently, and those where α SX is fixed to the value determined within PBE, yield results of comparable accuracy. Perturbative G 0W 0 corrections of eigenvalues obtained with self-consistent αSX are small on average, for all molecules in the GW100 test set.« less

Performance and Self-Consistency of the Generalized Dielectric Dependent Hybrid Functional

DOE PAGES

Brawand, Nicholas P.; Govoni, Marco; Vörös, Márton; ...

2017-05-24

Here, we analyze the performance of the recently proposed screened exchange constant functional (SX) on the GW100 test set, and we discuss results obtained at different levels of self-consistency. The SX functional is a generalization of dielectric dependent hybrid functionals to finite systems; it is nonempirical and depends on the average screening of the exchange interaction. We compare results for ionization potentials obtained with SX to those of CCSD(T) calculations and experiments, and we find excellent agreement, on par with recent state of the art methods based on many body perturbation theory. Applying SX perturbatively to correct PBE eigenvalues yieldsmore » improved results in most cases, except for ionic molecules, for which wave function self-consistency is instead crucial. Calculations where wave functions and the screened exchange constant (α SX) are determined self-consistently, and those where α SX is fixed to the value determined within PBE, yield results of comparable accuracy. Perturbative G 0W 0 corrections of eigenvalues obtained with self-consistent αSX are small on average, for all molecules in the GW100 test set.« less

Interaction between colloidal particles on an oil-water interface in dilute and dense phases.

PubMed

Parolini, Lucia; Law, Adam D; Maestro, Armando; Buzza, D Martin A; Cicuta, Pietro

2015-05-20

The interaction between micron-sized charged colloidal particles at polar/non-polar liquid interfaces remains surprisingly poorly understood for a relatively simple physical chemistry system. By measuring the pair correlation function g(r) for different densities of polystyrene particles at the decane-water interface, and using a powerful predictor-corrector inversion scheme, effective pair-interaction potentials can be obtained up to fairly high densities, and these reproduce the experimental g(r) in forward simulations, so are self consistent. While at low densities these potentials agree with published dipole-dipole repulsion, measured by various methods, an apparent density dependence and long range attraction are obtained when the density is higher. This condition is thus explored in an alternative fashion, measuring the local mobility of colloids when confined by their neighbors. This method of extracting interaction potentials gives results that are consistent with dipolar repulsion throughout the concentration range, with the same magnitude as in the dilute limit. We are unable to rule out the density dependence based on the experimental accuracy of our data, but we show that incomplete equilibration of the experimental system, which would be possible despite long waiting times due to the very strong repulsions, is a possible cause of artefacts in the inverted potentials. We conclude that to within the precision of these measurements, the dilute pair potential remains valid at high density in this system.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hansen, Stephanie B.; Harding, Eric C.; Knapp, Patrick F.

The burning core of an inertial confinement fusion (ICF) plasma produces bright x-rays at stagnation that can directly diagnose core conditions essential for comparison to simulations and understanding fusion yields. These x-rays also backlight the surrounding shell of warm, dense matter, whose properties are critical to understanding the efficacy of the inertial confinement and global morphology. In this work, we show that the absorption and fluorescence spectra of mid-Z impurities or dopants in the warm dense shell can reveal the optical depth, temperature, and density of the shell and help constrain models of warm, dense matter. This is illustrated bymore » the example of a high-resolution spectrum collected from an ICF plasma with a beryllium shell containing native iron impurities. Lastly, analysis of the iron K-edge provides model-independent diagnostics of the shell density (2.3 × 10 24 e/cm 3) and temperature (10 eV), while a 12-eV red shift in Kβ and 5-eV blue shift in the K-edge discriminate among models of warm dense matter: Both shifts are well described by a self-consistent field model based on density functional theory but are not fully consistent with isolated-atom models using ad-hoc density effects.« less

Fluorescence and absorption spectroscopy for warm dense matter studies and ICF plasma diagnostics

NASA Astrophysics Data System (ADS)

Hansen, S. B.; Harding, E. C.; Knapp, P. F.; Gomez, M. R.; Nagayama, T.; Bailey, J. E.

2018-05-01

The burning core of an inertial confinement fusion (ICF) plasma produces bright x-rays at stagnation that can directly diagnose core conditions essential for comparison to simulations and understanding fusion yields. These x-rays also backlight the surrounding shell of warm, dense matter, whose properties are critical to understanding the efficacy of the inertial confinement and global morphology. We show that the absorption and fluorescence spectra of mid-Z impurities or dopants in the warm dense shell can reveal the optical depth, temperature, and density of the shell and help constrain models of warm, dense matter. This is illustrated by the example of a high-resolution spectrum collected from an ICF plasma with a beryllium shell containing native iron impurities. Analysis of the iron K-edge provides model-independent diagnostics of the shell density (2.3 × 1024 e/cm3) and temperature (10 eV), while a 12-eV red shift in Kβ and 5-eV blue shift in the K-edge discriminate among models of warm dense matter: Both shifts are well described by a self-consistent field model based on density functional theory but are not fully consistent with isolated-atom models using ad-hoc density effects.

The Vibrational Frequencies of CaO2, ScO2, and TiO2: A Comparison of Theoretical Methods

NASA Technical Reports Server (NTRS)

Rosi, Marzio; Bauschlicher, Charles W., Jr.; Chertihin, George V.; Andrews, Lester; Arnold, James O. (Technical Monitor)

1997-01-01

The vibrational frequencies of several states of CaO2, ScO2, and TiO2 are computed at using density functional theory (DFT), the Hatree-Fock approach, second order Moller-Plesset perturbation theory (MP2), and the complete-active-space self-consistent-field theory. Three different functionals are used in the DFT calculations, including two hybrid functionals. The coupled cluster singles and doubles approach including the effect of unlinked triples, determined using perturbation theory, is applied to selected states. The Becke-Perdew 86 functional appears to be the cost effective method of choice, although even this functional does not perform well for one state of CaO2. The MP2 approach is significantly inferior to the DFT approaches.

Basis sets for the calculation of core-electron binding energies

NASA Astrophysics Data System (ADS)

Hanson-Heine, Magnus W. D.; George, Michael W.; Besley, Nicholas A.

2018-05-01

Core-electron binding energies (CEBEs) computed within a Δ self-consistent field approach require large basis sets to achieve convergence with respect to the basis set limit. It is shown that supplementing a basis set with basis functions from the corresponding basis set for the element with the next highest nuclear charge (Z + 1) provides basis sets that give CEBEs close to the basis set limit. This simple procedure provides relatively small basis sets that are well suited for calculations where the description of a core-ionised state is important, such as time-dependent density functional theory calculations of X-ray emission spectroscopy.

The Structure of Li7 and K7

NASA Technical Reports Server (NTRS)

Bauschlicher. Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

The self-consistent-field (SCF) approach and density functional theory, using the B3LYP hybrid functional, yield three low-lying structures for Li7(-). The relative separations differ for the SCF and B3LYP approaches, however the B3LYP results are in good agreement with the coupled cluster results. For K7(-), only an octahedron with one face capped is found to be a minimum; this the second most stable structure for Li7(-). A comparison of the computed separations between the low-lying states of K7 and the photoelectron detachment spectra does not allow an unambiguous assignment of the structure of K7(-).

Hyperfine coupling constants of the nitrogen and phosphorus atoms: A challenge for exact-exchange density-functional and post-Hartree-Fock methods

NASA Astrophysics Data System (ADS)

Kaupp, Martin; Arbuznikov, Alexei V.; Heßelmann, Andreas; Görling, Andreas

2010-05-01

The isotropic hyperfine coupling constants of the free N(S4) and P(S4) atoms have been evaluated with high-level post-Hartree-Fock and density-functional methods. The phosphorus hyperfine coupling presents a significant challenge to both types of methods. With large basis sets, MP2 and coupled-cluster singles and doubles calculations give much too small values for the phosphorus atom. Triple excitations are needed in coupled-cluster calculations to achieve reasonable agreement with experiment. None of the standard density functionals reproduce even the correct sign of this hyperfine coupling. Similarly, the computed hyperfine couplings depend crucially on the self-consistent treatment in exact-exchange density-functional theory within the optimized effective potential (OEP) method. Well-balanced auxiliary and orbital basis sets are needed for basis-expansion exact-exchange-only OEP approaches to come close to Hartree-Fock or numerical OEP data. Results from the localized Hartree-Fock and Krieger-Li-Iafrate approximations deviate notably from exact OEP data in spite of very similar total energies. Of the functionals tested, only full exact-exchange methods augmented by a correlation functional gave at least the correct sign of the P(S4) hyperfine coupling but with too low absolute values. The subtle interplay between the spin-polarization contributions of the different core shells has been analyzed, and the influence of even very small changes in the exchange-correlation potential could be identified.

Density functional theory studies of HCOOH decomposition on Pd(111)

DOE PAGES

Scaranto, Jessica; Mavrikakis, Manos

2015-12-02

Here, 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 CO 2 + H 2 and dehydration to CO + H 2O through the carboxyl (COOH) and formate (HCOO) intermediates. Our results suggest that HCOO formation is easiermore » than COOH formation, but HCOO decomposition is more difficult than COOH decomposition, in particular in presence of co-adsorbed O and OH species. Therefore, both paths may contribute to HCOOH decomposition. CO formation goes mainly through COOH decomposition.« less

Density functional tight-binding and infrequent metadynamics can capture entropic effects in intramolecular hydrogen transfer reactions

NASA Astrophysics Data System (ADS)

Oliveira, Luiz F. L.; Fu, Christopher D.; Pfaendtner, Jim

2018-04-01

Infrequent metadynamics uses biased simulations to estimate the unbiased kinetics of a system, facilitating the calculation of rates and barriers. Here the method is applied to study intramolecular hydrogen transfer reactions involving peroxy radicals, a class of reactions that is challenging to model due to the entropic contributions of the formation of ring structures in the transition state. Using the self-consistent charge density-functional based tight-binding (DFTB) method, we applied infrequent metadynamics to the study of four intramolecular H-transfer reactions, demonstrating that the method can qualitatively reproduce these high entropic contributions, as observed in experiments and those predicted by transition state theory modeled by higher levels of theory. We also show that infrequent metadynamics and DFTB are successful in describing the relationship between transition state ring size and kinetic coefficients (e.g., activation energies and the pre-exponential factors).

Atomically thin heterostructures based on single-layer tungsten diselenide and graphene.

PubMed

Lin, Yu-Chuan; Chang, Chih-Yuan S; Ghosh, Ram Krishna; Li, Jie; Zhu, Hui; Addou, Rafik; Diaconescu, Bogdan; Ohta, Taisuke; Peng, Xin; Lu, Ning; Kim, Moon J; Robinson, Jeremy T; Wallace, Robert M; Mayer, Theresa S; Datta, Suman; Li, Lain-Jong; Robinson, Joshua A

2014-12-10

Heterogeneous engineering of two-dimensional layered materials, including metallic graphene and semiconducting transition metal dichalcogenides, presents an exciting opportunity to produce highly tunable electronic and optoelectronic systems. In order to engineer pristine layers and their interfaces, epitaxial growth of such heterostructures is required. We report the direct growth of crystalline, monolayer tungsten diselenide (WSe2) on epitaxial graphene (EG) grown from silicon carbide. Raman spectroscopy, photoluminescence, and scanning tunneling microscopy confirm high-quality WSe2 monolayers, whereas transmission electron microscopy shows an atomically sharp interface, and low energy electron diffraction confirms near perfect orientation between WSe2 and EG. Vertical transport measurements across the WSe2/EG heterostructure provides evidence that an additional barrier to carrier transport beyond the expected WSe2/EG band offset exists due to the interlayer gap, which is supported by theoretical local density of states (LDOS) calculations using self-consistent density functional theory (DFT) and nonequilibrium Green's function (NEGF).

Fission barriers from multidimensionally-constrained covariant density functional theories

NASA Astrophysics Data System (ADS)

Lu, Bing-Nan; Zhao, Jie; Zhao, En-Guang; Zhou, Shan-Gui

2017-11-01

In recent years, we have developed the multidimensionally-constrained covariant density functional theories (MDC-CDFTs) in which both axial and spatial reflection symmetries are broken and all shape degrees of freedom described by βλμ with even μ, such as β20, β22, β30, β32, β40, etc., are included self-consistently. The MDC-CDFTs have been applied to the investigation of potential energy surfaces and fission barriers of actinide nuclei, third minima in potential energy surfaces of light actinides, shapes and potential energy surfaces of superheavy nuclei, octupole correlations between multiple chiral doublet bands in 78Br, octupole correlations in Ba isotopes, the Y32 correlations in N = 150 isotones and Zr isotopes, the spontaneous fission of Fm isotopes, and shapes of hypernuclei. In this contribution we present the formalism of MDC-CDFTs and the application of these theories to the study of fission barriers and potential energy surfaces of actinide nuclei.

Performance of the DFTB method in comparison to DFT and semiempirical methods for geometries and energies of C20-C86fullerene isomers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Guishan; Irle, Stephan; Morokuma, Keiji

2005-07-20

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. The performance of both non-iterative (NCC) and self-consistent charge (SCC) versions of the density functional tight binding (DFTB) method, as well as AM1 and PM3 methods, has been compared with the B3LYP method, a hybrid density functional theory (DFT) method, for equilibrium geometries and relative energies of various isomers of C20–C86 fullerenes. Both NCC- and SCCDFTB methods compare very favorablymore » with B3LYP both in geometries and isomer relative energies, while AM1 and PM3 do noticeably worse.« less

Density functional theory studies of HCOOH decomposition on Pd(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scaranto, Jessica; Mavrikakis, Manos

Here, 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 CO 2 + H 2 and dehydration to CO + H 2O through the carboxyl (COOH) and formate (HCOO) intermediates. Our results suggest that HCOO formation is easiermore » than COOH formation, but HCOO decomposition is more difficult than COOH decomposition, in particular in presence of co-adsorbed O and OH species. Therefore, both paths may contribute to HCOOH decomposition. CO formation goes mainly through COOH decomposition.« less

A new efficient method for calculation of Frenkel exciton parameters in molecular aggregates

NASA Astrophysics Data System (ADS)

Plötz, Per-Arno; Niehaus, Thomas; Kühn, Oliver

2014-05-01

The Frenkel exciton Hamiltonian is at the heart of many simulations of excitation energy transfer in molecular aggregates. It separates the aggregate into Coulomb-coupled monomers. Here it is shown that the respective parameters, i.e., monomeric excitation energies and Coulomb couplings between transition densities can be efficiently calculated using time-dependent tight-binding-based density functional theory (TD-DFTB). Specifically, Coulomb couplings are expressed in terms of self-consistently determined Mulliken transition charges. The approach is applied to two dimer systems. First, formaldehyde oxime for which a detailed comparison with standard DFT using the B3LYP and the PBE functionals as well as with SCS-CC2 is provided. Second, the Coulomb coupling is explored in dependence on the intermolecular coordinates for a perylene bisimide dimer. This provides structural evidence for the previously observed biphasic aggregation behavior of this dye.

The Mott transition in the strong coupling perturbation theory

NASA Astrophysics Data System (ADS)

Sherman, A.

2015-01-01

Using the strong coupling diagram technique a self-consistent equation for the electron Green's function is derived for the repulsive Hubbard model. Terms of two lowest orders of the ratio of the bandwidth Δ to the Hubbard repulsion U are taken into account in the irreducible part of the Larkin equation. The obtained equation is shown to retain causality and reduces to Green's function of uncorrelated electrons in the limit U → 0. Calculations were performed for the semi-elliptical initial band. It is shown that the approximation describes the Mott transition, which occurs at Uc =√{ 3 } Δ / 2. This value coincides with that obtained in the Hubbard-III approximation. At half-filling, for 0 < U Uc the Mott gap disappears.

Efficient mixing scheme for self-consistent all-electron charge density

NASA Astrophysics Data System (ADS)

Shishidou, Tatsuya; Weinert, Michael

2015-03-01

In standard ab initio density-functional theory calculations, the charge density ρ is gradually updated using the ``input'' and ``output'' densities of the current and previous iteration steps. To accelerate the convergence, Pulay mixing has been widely used with great success. It expresses an ``optimal'' input density ρopt and its ``residual'' Ropt by a linear combination of the densities of the iteration sequences. In large-scale metallic systems, however, the long range nature of Coulomb interaction often causes the ``charge sloshing'' phenomenon and significantly impacts the convergence. Two treatments, represented in reciprocal space, are known to suppress the sloshing: (i) the inverse Kerker metric for Pulay optimization and (ii) Kerker-type preconditioning in mixing Ropt. In all-electron methods, where the charge density does not have a converging Fourier representation, treatments equivalent or similar to (i) and (ii) have not been described so far. In this work, we show that, by going through the calculation of Hartree potential, one can accomplish the procedures (i) and (ii) without entering the reciprocal space. Test calculations are done with a FLAPW method.

The Thomas-Fermi model in the theory of systems of charged particles above the surface of liquid dielectrics

NASA Astrophysics Data System (ADS)

Lytvtnenko, D. M.; Slyusarenko, Yu. V.; Kirdin, A. I.

2012-10-01

A consistent theory of equilibrium states of same sign charges above the surface of liquid dielectric film located on solid substrate in the presence of external attracting constant electric field is proposed. The approach to the development of the theory is based on the Thomas-Fermi model generalized to the systems under consideration and on the variational principle. The using of self-consistent field model allows formulating a theory containing no adjustable constants. In the framework of the variational principle we obtain the self-consistency equations for the parameters describing the system: the distribution function of charges above the liquid dielectric surface, the electrostatic field potentials in all regions of the system and the surface profile of the liquid dielectric. The self-consistency equations are used to describe the phase transition associated with the formation of spatially periodic structures in the system of charges on liquid dielectric surface. Assuming the non-degeneracy of the gas of charges above the surface of liquid dielectric film the solutions of the self-consistency equations near the critical point are obtained. In the case of the symmetric phase we obtain the expressions for the potentials and electric fields in all regions of the studied system. The distribution of the charges above the surface of liquid dielectric film for the symmetric phase is derived. The system parameters of the phase transition to nonsymmetric phase - the states with a spatially periodic ordering are obtained. We derive the expression determining the period of two-dimensional lattice as a function of physical parameters of the problem - the temperature, the external attractive electric field, the number of electrons per unit of the flat surface area of the liquid dielectric, the density of the dielectric, its surface tension and permittivity, and the permittivity of the solid substrate. The possibility of generalizing the developed theory in the case of degenerate gas of like-charged particles above the liquid dielectric surface is discussed.

Simulation of Mach Probes in Non-Uniform Magnetized Plasmas: the Influence of a Background Density Gradient

NASA Astrophysics Data System (ADS)

Haakonsen, Christian Bernt; Hutchinson, Ian H.

2013-10-01

Mach probes can be used to measure transverse flow in magnetized plasmas, but what they actually measure in strongly non-uniform plasmas has not been definitively established. A fluid treatment in previous work has suggested that the diamagnetic drifts associated with background density and temperature gradients affect transverse flow measurements, but detailed computational study is required to validate and elaborate on those results; it is really a kinetic problem, since the probe deforms and introduces voids in the ion and electron distribution functions. A new code, the Plasma-Object Simulator with Iterated Trajectories (POSIT) has been developed to self-consistently compute the steady-state six-dimensional ion and electron distribution functions in the perturbed plasma. Particle trajectories are integrated backwards in time to the domain boundary, where arbitrary background distribution functions can be specified. This allows POSIT to compute the ion and electron density at each node of its unstructured mesh, update the potential based on those densities, and then iterate until convergence. POSIT is used to study the impact of a background density gradient on transverse Mach probe measurements, and the results compared to the previous fluid theory. C.B. Haakonsen was supported in part by NSF/DOE Grant No. DE-FG02-06ER54512, and in part by an SCGF award administered by ORISE under DOE Contract No. DE-AC05-06OR23100.

N-body simulations for f(R) gravity using a self-adaptive particle-mesh code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao Gongbo; Koyama, Kazuya; Li Baojiu

2011-02-15

We perform high-resolution N-body simulations for f(R) gravity based on a self-adaptive particle-mesh code MLAPM. The chameleon mechanism that recovers general relativity on small scales is fully taken into account by self-consistently solving the nonlinear equation for the scalar field. We independently confirm the previous simulation results, including the matter power spectrum, halo mass function, and density profiles, obtained by Oyaizu et al.[Phys. Rev. D 78, 123524 (2008)] and Schmidt et al.[Phys. Rev. D 79, 083518 (2009)], and extend the resolution up to k{approx}20 h/Mpc for the measurement of the matter power spectrum. Based on our simulation results, we discussmore » how the chameleon mechanism affects the clustering of dark matter and halos on full nonlinear scales.« less

Structural, Electronic and Elastic Properties of Half-Heusler Alloys CrNiZ (Z = Al, Si, Ge and As)

NASA Astrophysics Data System (ADS)

Zitouni, A.; Benstaali, W.; Abbad, A.; Lantri, T.; Bouadjemi, B.; Aziz, Z.

2018-06-01

In the present work, a self-consistent ab-initio calculation using the full- potential linearized augmented plane wave (FP-LAPW) method within the framework of the spin-polarized density functional theory (DFT) was used to study the structural, electronic, magnetic and elastic properties of the half Heusler alloys CrNiZ (Z = Al, Si, Ge and As) in three phases ( α, β and γ phases). The generalized gradient approximation (GGA) described by Perdew-Burke-Ernzerhof (PBE) was used. The results obtained for the spin-polarized band structure and the density of states show a halfmetallic behavior for the four compounds. The elastic constants ( C ij ) show that our compounds are ductile, stiff and anisotropic.

Antiplane shear wave propagation in fiber-reinforced composites.

PubMed

Kim, Jin-Yeon

2003-05-01

A self-consistent method for analyzing antiplane shear wave propagation in two-dimensional inhomogeneous media is presented. For applications in the high-frequency range, the self-consistent condition for the effective medium is solved being supplemented with the theory of quasidynamic effective density. Comparisons with other theoretical calculations and experimental data for fiber-reinforced composites demonstrate the merits of using the present method.

Higher-order finite-difference formulation of periodic Orbital-free Density Functional Theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Swarnava; Suryanarayana, Phanish, E-mail: phanish.suryanarayana@ce.gatech.edu

2016-02-15

We present a real-space formulation and higher-order finite-difference implementation of periodic Orbital-free Density Functional Theory (OF-DFT). Specifically, utilizing a local reformulation of the electrostatic and kernel terms, we develop a generalized framework for performing OF-DFT simulations with different variants of the electronic kinetic energy. In particular, we propose a self-consistent field (SCF) type fixed-point method for calculations involving linear-response kinetic energy functionals. In this framework, evaluation of both the electronic ground-state and forces on the nuclei are amenable to computations that scale linearly with the number of atoms. We develop a parallel implementation of this formulation using the finite-difference discretization.more » We demonstrate that higher-order finite-differences can achieve relatively large convergence rates with respect to mesh-size in both the energies and forces. Additionally, we establish that the fixed-point iteration converges rapidly, and that it can be further accelerated using extrapolation techniques like Anderson's mixing. We validate the accuracy of the results by comparing the energies and forces with plane-wave methods for selected examples, including the vacancy formation energy in Aluminum. Overall, the suitability of the proposed formulation for scalable high performance computing makes it an attractive choice for large-scale OF-DFT calculations consisting of thousands of atoms.« less

Plant interactions alter the predictions of metabolic scaling theory.

PubMed

Lin, Yue; Berger, Uta; Grimm, Volker; Huth, Franka; Weiner, Jacob

2013-01-01

Metabolic scaling theory (MST) is an attempt to link physiological processes of individual organisms with macroecology. It predicts a power law relationship with an exponent of -4/3 between mean individual biomass and density during density-dependent mortality (self-thinning). Empirical tests have produced variable results, and the validity of MST is intensely debated. MST focuses on organisms' internal physiological mechanisms but we hypothesize that ecological interactions can be more important in determining plant mass-density relationships induced by density. We employ an individual-based model of plant stand development that includes three elements: a model of individual plant growth based on MST, different modes of local competition (size-symmetric vs. -asymmetric), and different resource levels. Our model is consistent with the observed variation in the slopes of self-thinning trajectories. Slopes were significantly shallower than -4/3 if competition was size-symmetric. We conclude that when the size of survivors is influenced by strong ecological interactions, these can override predictions of MST, whereas when surviving plants are less affected by interactions, individual-level metabolic processes can scale up to the population level. MST, like thermodynamics or biomechanics, sets limits within which organisms can live and function, but there may be stronger limits determined by ecological interactions. In such cases MST will not be predictive.

Optical forces, torques, and force densities calculated at a microscopic level using a self-consistent hydrodynamics method

NASA Astrophysics Data System (ADS)

Ding, Kun; Chan, C. T.

2018-04-01

The calculation of optical force density distribution inside a material is challenging at the nanoscale, where quantum and nonlocal effects emerge and macroscopic parameters such as permittivity become ill-defined. We demonstrate that the microscopic optical force density of nanoplasmonic systems can be defined and calculated using the microscopic fields generated using a self-consistent hydrodynamics model that includes quantum, nonlocal, and retardation effects. We demonstrate this technique by calculating the microscopic optical force density distributions and the optical binding force induced by external light on nanoplasmonic dimers. This approach works even in the limit when the nanoparticles are close enough to each other so that electron tunneling occurs, a regime in which classical electromagnetic approach fails completely. We discover that an uneven distribution of optical force density can lead to a light-induced spinning torque acting on individual particles. The hydrodynamics method offers us an accurate and efficient approach to study optomechanical behavior for plasmonic systems at the nanoscale.

A self-consistent density based embedding scheme applied to the adsorption of CO on Pd(111)

NASA Astrophysics Data System (ADS)

Lahav, D.; Klüner, T.

2007-06-01

We derive a variant of a density based embedded cluster approach as an improvement to a recently proposed embedding theory for metallic substrates (Govind et al 1999 J. Chem. Phys. 110 7677; Klüner et al 2001 Phys. Rev. Lett. 86 5954). In this scheme, a local region in space is represented by a small cluster which is treated by accurate quantum chemical methodology. The interaction of the cluster with the infinite solid is taken into account by an effective one-electron embedding operator representing the surrounding region. We propose a self-consistent embedding scheme which resolves intrinsic problems of the former theory, in particular a violation of strict density conservation. The proposed scheme is applied to the well-known benchmark system CO/Pd(111).

Torsion as a source of expansion in a Bianchi type-I universe in the self-consistent Einstein-Cartan theory of a perfect fluid with spin density

NASA Technical Reports Server (NTRS)

Bradas, James C.; Fennelly, Alphonsus J.; Smalley, Larry L.

1987-01-01

It is shown that a generalized (or 'power law') inflationary phase arises naturally and inevitably in a simple (Bianchi type-I) anisotropic cosmological model in the self-consistent Einstein-Cartan gravitation theory with the improved stress-energy-momentum tensor with the spin density of Ray and Smalley (1982, 1983). This is made explicit by an analytical solution of the field equations of motion of the fluid variables. The inflation is caused by the angular kinetic energy density due to spin. The model further elucidates the relationship between fluid vorticity, the angular velocity of the inertially dragged tetrads, and the precession of the principal axes of the shear ellipsoid. Shear is not effective in damping the inflation.

Nonorthogonal orbital based N-body reduced density matrices and their applications to valence bond theory. I. Hamiltonian matrix elements between internally contracted excited valence bond wave functions

NASA Astrophysics Data System (ADS)

Chen, Zhenhua; Chen, Xun; Wu, Wei

2013-04-01

In this series, the n-body reduced density matrix (n-RDM) approach for nonorthogonal orbitals and their applications to ab initio valence bond (VB) methods are presented. As the first paper of this series, Hamiltonian matrix elements between internally contracted VB wave functions are explicitly provided by means of nonorthogonal orbital based RDM approach. To this end, a more generalized Wick's theorem, called enhanced Wick's theorem, is presented both in arithmetical and in graphical forms, by which the deduction of expressions for the matrix elements between internally contracted VB wave functions is dramatically simplified, and the matrix elements are finally expressed in terms of tensor contractions of electronic integrals and n-RDMs of the reference VB self-consistent field wave function. A string-based algorithm is developed for the purpose of evaluating n-RDMs in an efficient way. Using the techniques presented in this paper, one is able to develop new methods and efficient algorithms for nonorthogonal orbital based many-electron theory much easier than by use of the first quantized formulism.

Cyclic density functional theory: A route to the first principles simulation of bending in nanostructures

NASA Astrophysics Data System (ADS)

Banerjee, Amartya S.; Suryanarayana, Phanish

2016-11-01

We formulate and implement Cyclic Density Functional Theory (Cyclic DFT) - a self-consistent first principles simulation method for nanostructures with cyclic symmetries. Using arguments based on Group Representation Theory, we rigorously demonstrate that the Kohn-Sham eigenvalue problem for such systems can be reduced to a fundamental domain (or cyclic unit cell) augmented with cyclic-Bloch boundary conditions. Analogously, the equations of electrostatics appearing in Kohn-Sham theory can be reduced to the fundamental domain augmented with cyclic boundary conditions. By making use of this symmetry cell reduction, we show that the electronic ground-state energy and the Hellmann-Feynman forces on the atoms can be calculated using quantities defined over the fundamental domain. We develop a symmetry-adapted finite-difference discretization scheme to obtain a fully functional numerical realization of the proposed approach. We verify that our formulation and implementation of Cyclic DFT is both accurate and efficient through selected examples. The connection of cyclic symmetries with uniform bending deformations provides an elegant route to the ab-initio study of bending in nanostructures using Cyclic DFT. As a demonstration of this capability, we simulate the uniform bending of a silicene nanoribbon and obtain its energy-curvature relationship from first principles. A self-consistent ab-initio simulation of this nature is unprecedented and well outside the scope of any other systematic first principles method in existence. Our simulations reveal that the bending stiffness of the silicene nanoribbon is intermediate between that of graphene and molybdenum disulphide - a trend which can be ascribed to the variation in effective thickness of these materials. We describe several future avenues and applications of Cyclic DFT, including its extension to the study of non-uniform bending deformations and its possible use in the study of the nanoscale flexoelectric effect.

Holographic scalar fields in Kaluza-Klein framework

NASA Astrophysics Data System (ADS)

Erkan, Sevda; Pirinccioglu, Nurettin; Salti, Mustafa; Aydogdu, Oktay

2017-12-01

Making use of the Friedmann-Robertson-Walker (FRW) type Kaluza-Klein universe (KKU), we discuss the holographic dark energy density (HDED) in order to develop its correspondence with some scalar field descriptions such as the tachyon, quintessence, DBI-essence, dilaton and the k-essence. It is concluded that the Kaluza-Klein-type HDED proposal becomes stable throughout the history of our universe and is consistent with the current status of the universe. Next, we obtain the exact solutions of self-interacting potential and scalar field function for the selected models.

First-principles phase stability at high temperatures and pressure in Nb 90Zr 10 alloy

DOE PAGES

Landa, A.; Soderlind, P.

2016-08-18

The phase stability of Nb 90Zr 10 alloy at high temperatures and compression is explored by means of first-principles electronic-structure calculations. Utilizing the self-consistent ab initio lattice dynamics (SCAILD) approach in conjunction with density-functional theory, we show that pressure-induced mechanical instability of the body-centered cubic phase, which results in formation of a rhombohedral phase at around 50 GPa, will prevail significant heating. As a result, the body-centered cubic structure will recover before melting at ~1800 K.

Self-interaction-corrected time-dependent density-functional-theory calculations of x-ray-absorption spectra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tu, Guangde; Rinkevicius, Zilvinas; Vahtras, Olav

We outline an approach within time-dependent density functional theory that predicts x-ray spectra on an absolute scale. The approach rests on a recent formulation of the resonant-convergent first-order polarization propagator [P. Norman et al., J. Chem. Phys. 123, 194103 (2005)] and corrects for the self-interaction energy of the core orbital. This polarization propagator approach makes it possible to directly calculate the x-ray absorption cross section at a particular frequency without explicitly addressing the excited-state spectrum. The self-interaction correction for the employed density functional accounts for an energy shift of the spectrum, and fully correlated absolute-scale x-ray spectra are thereby obtainedmore » based solely on optimization of the electronic ground state. The procedure is benchmarked against experimental spectra of a set of small organic molecules at the carbon, nitrogen, and oxygen K edges.« less

A practical guide to density matrix embedding theory in quantum chemistry

DOE PAGES

Wouters, Sebastian; Jimenez-Hoyos, Carlos A.; Sun, Qiming; ...

2016-05-09

Density matrix embedding theory (DMET) (Knizia, G.; Chan, G. K.-L. Phys. Rev. Lett. 2012, 109, 186404) provides a theoretical framework to treat finite fragments in the presence of a surrounding molecular or bulk environment, even when there is significant correlation or entanglement between the two. In this work, we give a practically oriented and explicit description of the numerical and theoretical formulation of DMET. Here, we also describe in detail how to perform self-consistent DMET optimizations. We explore different embedding strategies with and without a self-consistency condition in hydrogen rings, beryllium rings, and a sample SN2 reaction.

Interplay between Self-Assembled Structures and Energy Level Alignment of Benzenediamine on Au(111) Surfaces

NASA Astrophysics Data System (ADS)

Li, Guo; Neaton, Jeffrey

2015-03-01

Using van der Waals-corrected density functional theory (DFT) calculations, we study the adsorption of benzene-diamine (BDA) molecules on Au(111) surfaces. We find that at low surface coverage, the adsorbed molecules prefer to stay isolated from each other in a monomer phase, due to the inter-molecular dipole-dipole repulsions. However, when the coverage rises above a critical value of 0.9nm-2, the adsorbed molecules aggregate into linear structures via hydrogen bonding between amine groups, consistent with recent experiments [Haxton, Zhou, Tamblyn, et al, Phys. Rev. Lett. 111, 265701 (2013)]. Moreover, we find that these linear structures at high density considerably reduces the Au work function (relative to a monomer phase). Due to reduced surface polarization effects, we estimate that the resonance energy of the highest occupied molecular orbital of the adsorbed BDA molecule relative to the Au Fermi level is significantly lower than the monomer phase by more than 0.5 eV, consistent with the experimental measurements [DellAngela, Kladnik, and Cossaro, et al., Nano Lett. 10, 2470 (2010)]. This work supported by DOE (the JCAP under Award Number DE-SC000499 and the Molecular Foundry of LBNL), and computational resources provided by NERSC.

Monte Carlo method for computing density of states and quench probability of potential energy and enthalpy landscapes.

PubMed

Mauro, John C; Loucks, Roger J; Balakrishnan, Jitendra; Raghavan, Srikanth

2007-05-21

The thermodynamics and kinetics of a many-body system can be described in terms of a potential energy landscape in multidimensional configuration space. The partition function of such a landscape can be written in terms of a density of states, which can be computed using a variety of Monte Carlo techniques. In this paper, a new self-consistent Monte Carlo method for computing density of states is described that uses importance sampling and a multiplicative update factor to achieve rapid convergence. The technique is then applied to compute the equilibrium quench probability of the various inherent structures (minima) in the landscape. The quench probability depends on both the potential energy of the inherent structure and the volume of its corresponding basin in configuration space. Finally, the methodology is extended to the isothermal-isobaric ensemble in order to compute inherent structure quench probabilities in an enthalpy landscape.

Ab-initio calculations of electronic, transport, and structural properties of boron phosphide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ejembi, J. I.; Nwigboji, I. H.; Franklin, L.

2014-09-14

We present results from ab-initio, self-consistent density functional theory calculations of electronic and related properties of zinc blende boron phosphide (zb-BP). We employed a local density approximation potential and implemented the linear combination of atomic orbitals formalism. This technique follows the Bagayoko, Zhao, and Williams method, as enhanced by the work of Ekuma and Franklin. The results include electronic energy bands, densities of states, and effective masses. The calculated band gap of 2.02 eV, for the room temperature lattice constant of a=4.5383 Å, is in excellent agreement with the experimental value of 2.02±0.05 eV. Our result for the bulk modulus,more » 155.7 GPa, agrees with experiment (152–155 GPa). Our predictions for the equilibrium lattice constant and the corresponding band gap, for very low temperatures, are 4.5269 Å and 2.01 eV, respectively.« less

Self-assembly in Dipolar Fluids

NASA Astrophysics Data System (ADS)

Ronti, Michela; Kantorovich, Sofia

We are studying low temperature structural transitions in dipolar hard spheres (DHS), combining grand-canonical Monte Carlo simulations and direct analytical theoretical calculations. DHS is characterized by long-range anisotropic interactions: it consists of a point dipole at the center of a hard sphere. We are interested in low temperature and low density phase behaviour of DHS systems. From a theoretical point of view the process of self-assembly is not responsible for a phase transition; this belief was completely reverted by theoretical studies showing that the process of self-assembly is alone capable to induce phase transition. On the other hand in the last years it was proved that no sign of critical behaviour is observed, implementing efficient and tailored Monte Carlo algorithms. Moreover a theoretical approach based on Density Functional Theory was developed: a series of structural transitions were discovered providing evidence of a hierarchy in the structures on cooling. We are performing free-energy calculations in order to draw the phase diagram of DHS model. Comparing the numerical results with the theoretical ones shed light on the scenario of temperature induced structural transitions in magnetic nanocolloids. Etn-COLLDENSE (H2020-MCSA-ITN-2014, Grant No. 642774).

On the relation between orbital-localization and self-interaction errors in the density functional theory treatment of organic semiconductors.

PubMed

Körzdörfer, T

2011-03-07

It is commonly argued that the self-interaction error (SIE) inherent in semilocal density functionals is related to the degree of the electronic localization. Yet at the same time there exists a latent ambiguity in the definitions of the terms "localization" and "self-interaction," which ultimately prevents a clear and readily accessible quantification of this relationship. This problem is particularly pressing for organic semiconductor molecules, in which delocalized molecular orbitals typically alternate with localized ones, thus leading to major distortions in the eigenvalue spectra. This paper discusses the relation between localization and SIEs in organic semiconductors in detail. Its findings provide further insights into the SIE in the orbital energies and yield a new perspective on the failure of self-interaction corrections that identify delocalized orbital densities with electrons. © 2011 American Institute of Physics.

Assessing the performance of self-consistent hybrid functional for band gap calculation in oxide semiconductors

NASA Astrophysics Data System (ADS)

He, Jiangang; Franchini, Cesare

2017-11-01

In this paper we assess the predictive power of the self-consistent hybrid functional scPBE0 in calculating the band gap of oxide semiconductors. The computational procedure is based on the self-consistent evaluation of the mixing parameter α by means of an iterative calculation of the static dielectric constant using the perturbation expansion after discretization method and making use of the relation \

A self-similar magnetohydrodynamic model for ball lightnings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsui, K. H.

2006-07-15

Ball lightning is modeled by magnetohydrodynamic (MHD) equations in two-dimensional spherical geometry with azimuthal symmetry. Dynamic evolutions in the radial direction are described by the self-similar evolution function y(t). The plasma pressure, mass density, and magnetic fields are solved in terms of the radial label {eta}. This model gives spherical MHD plasmoids with axisymmetric force-free magnetic field, and spherically symmetric plasma pressure and mass density, which self-consistently determine the polytropic index {gamma}. The spatially oscillating nature of the radial and meridional field structures indicate embedded regions of closed field lines. These regions are named secondary plasmoids, whereas the overall self-similarmore » spherical structure is named the primary plasmoid. According to this model, the time evolution function allows the primary plasmoid expand outward in two modes. The corresponding ejection of the embedded secondary plasmoids results in ball lightning offering an answer as how they come into being. The first is an accelerated expanding mode. This mode appears to fit plasmoids ejected from thundercloud tops with acceleration to ionosphere seen in high altitude atmospheric observations of sprites and blue jets. It also appears to account for midair high-speed ball lightning overtaking airplanes, and ground level high-speed energetic ball lightning. The second is a decelerated expanding mode, and it appears to be compatible to slowly moving ball lightning seen near ground level. The inverse of this second mode corresponds to an accelerated inward collapse, which could bring ball lightning to an end sometimes with a cracking sound.« less

Complexation of nicotinic acid with first generation poly(amidoamine) dendrimers: A microscopic view from density functional theory

NASA Astrophysics Data System (ADS)

Badalkhani-Khamseh, Farideh; Bahrami, Aidin; Ebrahim-Habibi, Azadeh; Hadipour, Nasser L.

2017-09-01

This study explains some electronic and structural parameters of niacin (NA) encapsulation into PAMAM-G1 dendrimer using DFT calculations. Optimized structural geometries, interaction energies, NMR, NBO, and AIM analyses, in accordance with experiment, revealed that the stability of G1@NA complex can be attributed to the five intermolecular hydrogen bonds formed between the functional groups of G1 and NA. Because of nearing to the experimental results, all the calculations repeated again using a self-consistent reaction field (SCRF) and the polarizable continuum model (PCM) to address the implicit solvent effects and the obtained results were in line with the calculations in gas phase.

Proton transfer pathways, energy landscape, and kinetics in creatine-water systems.

PubMed

Ivchenko, Olga; Whittleston, Chris S; Carr, Joanne M; Imhof, Petra; Goerke, Steffen; Bachert, Peter; Wales, David J

2014-02-27

We study the exchange processes of the metabolite creatine, which is present in both tumorous and normal tissues and has NH2 and NH groups that can transfer protons to water. Creatine produces chemical exchange saturation transfer (CEST) contrast in magnetic resonance imaging (MRI). The proton transfer pathway from zwitterionic creatine to water is examined using a kinetic transition network constructed from the discrete path sampling approach and an approximate quantum-chemical energy function, employing the self-consistent-charge density-functional tight-binding (SCC-DFTB) method. The resulting potential energy surface is visualized by constructing disconnectivity graphs. The energy landscape consists of two distinct regions corresponding to the zwitterionic creatine structures and deprotonated creatine. The activation energy that characterizes the proton transfer from the creatine NH2 group to water was determined from an Arrhenius fit of rate constants as a function of temperature, obtained from harmonic transition state theory. The result is in reasonable agreement with values obtained in water exchange spectroscopy (WEX) experiments.

Higher order alchemical derivatives from coupled perturbed self-consistent field theory.

PubMed

Lesiuk, Michał; Balawender, Robert; Zachara, Janusz

2012-01-21

We present an analytical approach to treat higher order derivatives of Hartree-Fock (HF) and Kohn-Sham (KS) density functional theory energy in the Born-Oppenheimer approximation with respect to the nuclear charge distribution (so-called alchemical derivatives). Modified coupled perturbed self-consistent field theory is used to calculate molecular systems response to the applied perturbation. Working equations for the second and the third derivatives of HF/KS energy are derived. Similarly, analytical forms of the first and second derivatives of orbital energies are reported. The second derivative of Kohn-Sham energy and up to the third derivative of Hartree-Fock energy with respect to the nuclear charge distribution were calculated. Some issues of practical calculations, in particular the dependence of the basis set and Becke weighting functions on the perturbation, are considered. For selected series of isoelectronic molecules values of available alchemical derivatives were computed and Taylor series expansion was used to predict energies of the "surrounding" molecules. Predicted values of energies are in unexpectedly good agreement with the ones computed using HF/KS methods. Presented method allows one to predict orbital energies with the error less than 1% or even smaller for valence orbitals. © 2012 American Institute of Physics

Axisymmetric Self-Consistent Model of the Solar Wind Interaction with the Lism: Basic Results and Possible Ways of Development

NASA Astrophysics Data System (ADS)

Baranov, V. B.; Malama, Yu. G.

1996-10-01

We analyze the main results of the axisymmetric self-consistent model of the solar wind (SW) and supersonic local interstellar medium (LISM) interaction proposed by Baranov and Malama (1993, hereafter BM93, 1995) for an interstellar flow assumed to be composed of protons, electrons and hydrogen atoms. Here, in addition to the resonant charge exchange we also take into account the photoionization and the ionization by electron impact. The characteristics of the plasma in the interface region and inside the heliosphere depend strongly on the ionization degree of the LISM. The distribution function of the H atoms which penetrate the solar system from the LISM is non-Maxwellian, which implies that a pure hydrodynamic description of their motion is not appropriate. The H atom number density is a non-monotonic function of the heliocentric distance and the existence of a “hydrogen wall” in the vicinity of the heliopause is important for the interpretation of solar Lyman-alpha scattering experiments. The influence of the interface plasma structure on the interstellar oxygen penetration into the solar system is also illustrated. Possible ways of development of the model are analyzed.

Rectification of graphene self-switching diodes: First-principles study

NASA Astrophysics Data System (ADS)

Ghaziasadi, Hassan; Jamasb, Shahriar; Nayebi, Payman; Fouladian, Majid

2018-05-01

The first principles calculations based on self-consistent charge density functional tight-binding have performed to investigate the electrical properties and rectification behavior of the graphene self-switching diodes (GSSD). The devices contained two structures called CG-GSSD and DG-GSSD which have metallic or semiconductor gates depending on their side gates have a single or double hydrogen edge functionalized. We have relaxed the devices and calculated I-V curves, transmission spectrums and maximum rectification ratios. We found that the DG-MSM devices are more favorable and more stable. Also, the DG-MSM devices have better maximum rectification ratios and current. Moreover, by changing the side gates widths and behaviors from semiconductor to metal, the threshold voltages under forward bias changed from +1.2 V to +0.3 V. Also, the maximum currents are obtained from 1.12 μA to 10.50 μA. Finally, the MSM and SSS type of all devices have minimum and maximum values of voltage threshold and maximum rectification ratios, but the 769-DG devices don't obey this rule.

A simple derivation of the exact quasiparticle theory and its extension to arbitrary initial excited eigenstates.

PubMed

Ohno, Kaoru; Ono, Shota; Isobe, Tomoharu

2017-02-28

The quasiparticle (QP) energies, which are minus of the energies required by removing or produced by adding one electron from/to the system, corresponding to the photoemission or inverse photoemission (PE/IPE) spectra, are determined together with the QP wave functions, which are not orthonormal and even not linearly independent but somewhat similar to the normal spin orbitals in the theory of the configuration interaction, by self-consistently solving the QP equation coupled with the equation for the self-energy. The electron density, kinetic, and all interaction energies can be calculated using the QP wave functions. We prove in a simple way that the PE/IPE spectroscopy and therefore this QP theory can be applied to an arbitrary initial excited eigenstate. In this proof, we show that the energy-dependence of the self-energy is not an essential difficulty, and the QP picture holds exactly if there is no relaxation mechanism in the system. The validity of the present theory for some initial excited eigenstates is tested using the one-shot GW approximation for several atoms and molecules.

Galaxy halo expansions: a new biorthogonal family of potential-density pairs

NASA Astrophysics Data System (ADS)

Lilley, Edward J.; Sanders, Jason L.; Evans, N. Wyn; Erkal, Denis

2018-05-01

Efficient expansions of the gravitational field of (dark) haloes have two main uses in the modelling of galaxies: first, they provide a compact representation of numerically constructed (or real) cosmological haloes, incorporating the effects of triaxiality, lopsidedness or other distortion. Secondly, they provide the basis functions for self-consistent field expansion algorithms used in the evolution of N-body systems. We present a new family of biorthogonal potential-density pairs constructed using the Hankel transform of the Laguerre polynomials. The lowest order density basis functions are double-power-law profiles cusped like ρ ˜ r-2+1/α at small radii with asymptotic density fall-off like ρ ˜ r-3-1/(2α). Here, α is a parameter satisfying α ≥ 1/2. The family therefore spans the range of inner density cusps found in numerical simulations, but has much shallower - and hence more realistic - outer slopes than the corresponding members of the only previously known family deduced by Zhao and exemplified by Hernquist & Ostriker. When α = 1, the lowest order density profile has an inner density cusp of ρ ˜ r-1 and an outer density slope of ρ ˜ r-3.5, similar to the famous Navarro, Frenk & White (NFW) model. For this reason, we demonstrate that our new expansion provides a more accurate representation of flattened NFW haloes than the competing Hernquist-Ostriker expansion. We utilize our new expansion by analysing a suite of numerically constructed haloes and providing the distributions of the expansion coefficients.

N-body simulations for f(R) gravity using a self-adaptive particle-mesh code

NASA Astrophysics Data System (ADS)

Zhao, Gong-Bo; Li, Baojiu; Koyama, Kazuya

2011-02-01

We perform high-resolution N-body simulations for f(R) gravity based on a self-adaptive particle-mesh code MLAPM. The chameleon mechanism that recovers general relativity on small scales is fully taken into account by self-consistently solving the nonlinear equation for the scalar field. We independently confirm the previous simulation results, including the matter power spectrum, halo mass function, and density profiles, obtained by Oyaizu [Phys. Rev. DPRVDAQ1550-7998 78, 123524 (2008)10.1103/PhysRevD.78.123524] and Schmidt [Phys. Rev. DPRVDAQ1550-7998 79, 083518 (2009)10.1103/PhysRevD.79.083518], and extend the resolution up to k˜20h/Mpc for the measurement of the matter power spectrum. Based on our simulation results, we discuss how the chameleon mechanism affects the clustering of dark matter and halos on full nonlinear scales.

Low-density homogeneous symmetric nuclear matter: Disclosing dinucleons in coexisting phases

NASA Astrophysics Data System (ADS)

Arellano, Hugo F.; Delaroche, Jean-Paul

2015-01-01

The effect of in-medium dinucleon bound states on self-consistent single-particle fields in Brueckner, Bethe and Goldstone theory is investigated in symmetric nuclear matter at zero temperature. To this end, dinucleon bound state occurences in the 1 S 0 and 3 SD 1 channels are explicitly accounted for --within the continuous choice for the auxiliary fields-- while imposing self-consistency in Brueckner-Hartree-Fock approximation calculations. Searches are carried out at Fermi momenta in the range fm-1, using the Argonne bare nucleon-nucleon potential without resorting to the effective-mass approximation. As a result, two distinct solutions meeting the self-consistency requirement are found with overlapping domains in the interval 0.130 fm-1 0.285 fm-1, corresponding to mass densities between and g cm-3. Effective masses as high as three times the nucleon mass are found in the coexistence domain. The emergence of superfluidity in relationship with BCS pairing gap solutions is discussed.

Statistical properties of swarms of self-propelled particles with repulsions across the order-disorder transition

NASA Astrophysics Data System (ADS)

Romenskyy, Maksym; Lobaskin, Vladimir

2013-03-01

We study dynamic self-organisation and order-disorder transitions in a two-dimensional system of self-propelled particles. Our model is a variation of the Vicsek model, where particles align the motion to their neighbours but repel each other at short distances. We use computer simulations to measure the orientational order parameter for particle velocities as a function of intensity of internal noise or particle density. We show that in addition to the transition to an ordered state on increasing the particle density, as reported previously, there exists a transition into a disordered phase at the higher densities, which can be attributed to the destructive action of the repulsions. We demonstrate that the transition into the ordered phase is accompanied by the onset of algebraic behaviour of the two-point velocity correlation function and by a non-monotonous variation of the velocity relaxation time. The critical exponent for the decay of the velocity correlation function in the ordered phase depends on particle concentration at low densities but assumes a universal value in more dense systems.

Self-crowding of AMPA receptors in the excitatory postsynaptic density can effectuate anomalous receptor sub-diffusion.

PubMed

Gupta, Rahul

2018-02-01

AMPA receptors (AMPARs) and their associations with auxiliary transmembrane proteins are bulky structures with large steric-exclusion volumes. Hence, self-crowding of AMPARs, depending on the local density, may affect their lateral diffusion in the postsynaptic membrane as well as in the highly crowded postsynaptic density (PSD) at excitatory synapses. Earlier theoretical studies considered only the roles of transmembrane obstacles and the AMPAR-binding submembranous scaffold proteins in shaping receptor diffusion within PSD. Using lattice model of diffusion, the present study investigates the additional impacts of self-crowding on the anomalousity and effective diffusion coefficient (Deff) of AMPAR diffusion. A recursive algorithm for avoiding false self-blocking during diffusion simulation is also proposed. The findings suggest that high density of AMPARs in the obstacle-free membrane itself engenders strongly anomalous diffusion and severe decline in Deff. Adding transmembrane obstacles to the membrane accentuates the anomalousity arising from self-crowding due to the reduced free diffusion space. Contrarily, enhanced AMPAR-scaffold binding, either through increase in binding strength or scaffold density or both, ameliorates the anomalousity resulting from self-crowding. However, binding has differential impacts on Deff depending on the receptor density. Increase in binding causes consistent decrease in Deff for low and moderate receptor density. For high density, binding increases Deff as long as it reduces anomalousity associated with intense self-crowding. Given a sufficiently strong binding condition when diffusion acquires normal behavior, further increase in binding causes decrease in Deff. Supporting earlier experimental observations are mentioned and implications of present findings to the experimental observations on AMPAR diffusion are also drawn.

A self-powered glucose biosensing system.

PubMed

Slaughter, Gymama; Kulkarni, Tanmay

2016-04-15

A self-powered glucose biosensor (SPGS) system is fabricated and in vitro characterization of the power generation and charging frequency characteristics in glucose analyte are described. The bioelectrodes consist of compressed network of three-dimensional multi-walled carbon nanotubes with redox enzymes, pyroquinoline quinone glucose dehydrogenase (PQQ-GDH) and laccase functioning as the anodic and cathodic catalyst, respectively. When operated in 45 mM glucose, the biofuel cell exhibited an open circuit voltage and power density of 681.8 mV and 67.86 µW/cm(2) at 335 mV, respectively, with a current density of 202.2 µA/cm(2). Moreover, at physiological glucose concentration (5mM), the biofuel cell exhibits open circuit voltage and power density of 302.1 mV and 15.98 µW/cm(2) at 166.3 mV, respectively, with a current density of 100 µA/cm(2). The biofuel cell assembly produced a linear dynamic range of 0.5-45 mM glucose. These findings show that glucose biofuel cells can be further investigated in the development of a self-powered glucose biosensor by using a capacitor as the transducer element. By monitoring the capacitor charging frequencies, which are influenced by the concentration of the glucose analyte, a linear dynamic range of 0.5-35 mM glucose is observed. The operational stability of SPGS is monitored over a period of 63 days and is found to be stable with 15.38% and 11.76% drop in power density under continuous discharge in 10mM and 20mM glucose, respectively. These results demonstrate that SPGSs can simultaneously generate bioelectricity to power ultra-low powered devices and sense glucose. Copyright © 2015 Elsevier B.V. All rights reserved.

Fluorescence and absorption spectroscopy for warm dense matter studies and ICF plasma diagnostics

DOE PAGES

Hansen, Stephanie B.; Harding, Eric C.; Knapp, Patrick F.; ...

2018-03-07

The burning core of an inertial confinement fusion (ICF) plasma produces bright x-rays at stagnation that can directly diagnose core conditions essential for comparison to simulations and understanding fusion yields. These x-rays also backlight the surrounding shell of warm, dense matter, whose properties are critical to understanding the efficacy of the inertial confinement and global morphology. In this work, we show that the absorption and fluorescence spectra of mid-Z impurities or dopants in the warm dense shell can reveal the optical depth, temperature, and density of the shell and help constrain models of warm, dense matter. This is illustrated bymore » the example of a high-resolution spectrum collected from an ICF plasma with a beryllium shell containing native iron impurities. Lastly, analysis of the iron K-edge provides model-independent diagnostics of the shell density (2.3 × 10 24 e/cm 3) and temperature (10 eV), while a 12-eV red shift in Kβ and 5-eV blue shift in the K-edge discriminate among models of warm dense matter: Both shifts are well described by a self-consistent field model based on density functional theory but are not fully consistent with isolated-atom models using ad-hoc density effects.« less

Extended Lagrangian Excited State Molecular Dynamics

DOE PAGES

Bjorgaard, Josiah August; Sheppard, Daniel Glen; Tretiak, Sergei; ...

2018-01-09

In this work, an extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born–Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a time-dependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both formore » the self-consistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. In conclusion, the XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree–Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).« less

Convergence of quasiparticle self-consistent GW calculations of transition metal monoxides

NASA Astrophysics Data System (ADS)

Das, Suvadip; Coulter, John E.; Manousakis, Efstratios

2015-03-01

We have investigated the electronic structure of the transition metal monoxides MnO, CoO, and NiO in their undistorted rock-salt structure within a fully iterated quasiparticle self-consistent GW (QPscGW) scheme. We have studied the convergence of the QPscGW method, i.e., how the quasiparticle energy eigenvalues and wavefunctions converge as a function of the QPscGW iterations, and compared the converged outputs obtained from different starting wavefunctions. We found that the convergence is slow and that a one-shot G0W0 calculation does not significantly improve the initial eigenvalues and states. In some cases the ``path'' to convergence may go through energy band reordering which cannot be captured by the simple initial unperturbed Hamiltonian. When a fully iterated solution is reached, the converged density of states, band-gaps and magnetic moments of these oxides are found to be only weakly dependent on the choice of the starting wavefunctions and in reasonable agreement with the experiment. National High Magnetic Field Laboratory.

Extended Lagrangian Excited State Molecular Dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bjorgaard, Josiah August; Sheppard, Daniel Glen; Tretiak, Sergei

In this work, an extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born–Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a time-dependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both formore » the self-consistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. In conclusion, the XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree–Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).« less

Extended Lagrangian Excited State Molecular Dynamics.

PubMed

Bjorgaard, J A; Sheppard, D; Tretiak, S; Niklasson, A M N

2018-02-13

An extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born-Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a time-dependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both for the self-consistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. The XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree-Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).

Modeling self-consistent multi-class dynamic traffic flow

NASA Astrophysics Data System (ADS)

Cho, Hsun-Jung; Lo, Shih-Ching

2002-09-01

In this study, we present a systematic self-consistent multiclass multilane traffic model derived from the vehicular Boltzmann equation and the traffic dispersion model. The multilane domain is considered as a two-dimensional space and the interaction among vehicles in the domain is described by a dispersion model. The reason we consider a multilane domain as a two-dimensional space is that the driving behavior of road users may not be restricted by lanes, especially motorcyclists. The dispersion model, which is a nonlinear Poisson equation, is derived from the car-following theory and the equilibrium assumption. Under the concept that all kinds of users share the finite section, the density is distributed on a road by the dispersion model. In addition, the dynamic evolution of the traffic flow is determined by the systematic gas-kinetic model derived from the Boltzmann equation. Multiplying Boltzmann equation by the zeroth, first- and second-order moment functions, integrating both side of the equation and using chain rules, we can derive continuity, motion and variance equation, respectively. However, the second-order moment function, which is the square of the individual velocity, is employed by previous researches does not have physical meaning in traffic flow. Although the second-order expansion results in the velocity variance equation, additional terms may be generated. The velocity variance equation we propose is derived from multiplying Boltzmann equation by the individual velocity variance. It modifies the previous model and presents a new gas-kinetic traffic flow model. By coupling the gas-kinetic model and the dispersion model, a self-consistent system is presented.

Extent of Fock-exchange mixing for a hybrid van der Waals density functional?

NASA Astrophysics Data System (ADS)

Jiao, Yang; Schröder, Elsebeth; Hyldgaard, Per

2018-05-01

The vdW-DF-cx0 exchange-correlation hybrid design [K. Berland et al., J. Chem. Phys. 146, 234106 (2017)] has a truly nonlocal correlation component and aims to facilitate concurrent descriptions of both covalent and non-covalent molecular interactions. The vdW-DF-cx0 design mixes a fixed ratio, a, of the Fock exchange into the consistent-exchange van der Waals density functional, vdW-DF-cx [K. Berland and P. Hyldgaard, Phys. Rev. B 89, 035412 (2014)]. The mixing value a is sometimes taken as a semi-empirical parameter in hybrid formulations. Here, instead, we assert a plausible optimum average a value for the vdW-DF-cx0 design from a formal analysis; A new, independent determination of the mixing a is necessary since the Becke fit [A. D. Becke, J. Chem. Phys. 98, 5648 (1993)], yielding a' = 0.2, is restricted to semilocal correlation and does not reflect non-covalent interactions. To proceed, we adapt the so-called two-legged hybrid construction [K. Burke et al., Chem. Phys. Lett. 265, 115 (1997)] to a starting point in the vdW-DF-cx functional. For our approach, termed vdW-DF-tlh, we estimate the properties of the adiabatic-connection specification of the exact exchange-correlation functional, by combining calculations of the Fock exchange and of the coupling-constant variation in vdW-DF-cx. We find that such vdW-DF-tlh hybrid constructions yield accurate characterizations of molecular interactions (even if they lack self-consistency). The accuracy motivates trust in the vdW-DF-tlh determination of system-specific values of the Fock-exchange mixing. We find that an average value a' = 0.2 best characterizes the vdW-DF-tlh description of covalent and non-covalent interactions, although there exists some scatter. This finding suggests that the original Becke value, a' = 0.2, also represents an optimal average Fock-exchange mixing for the new, truly nonlocal-correlation hybrids. To enable self-consistent calculations, we furthermore define and test a zero-parameter hybrid functional vdW-DF-cx0p (having fixed mixing a' = 0.2) and document that this truly nonlocal correlation hybrid works for general molecular interactions (at reference and at relaxed geometries). It is encouraging that the vdW-DF-cx0p functional remains useful also for descriptions of some extended systems.

Full-data Results of Hubble Frontier Fields: UV Luminosity Functions at z ∼ 6–10 and a Consistent Picture of Cosmic Reionization

NASA Astrophysics Data System (ADS)

Ishigaki, Masafumi; Kawamata, Ryota; Ouchi, Masami; Oguri, Masamune; Shimasaku, Kazuhiro; Ono, Yoshiaki

2018-02-01

We present UV luminosity functions of dropout galaxies at z∼ 6{--}10 with the complete Hubble Frontier Fields data. We obtain a catalog of ∼450 dropout-galaxy candidates (350, 66, and 40 at z∼ 6{--}7, 8, and 9, respectively), with UV absolute magnitudes that reach ∼ -14 mag, ∼2 mag deeper than the Hubble Ultra Deep Field detection limits. We carefully evaluate number densities of the dropout galaxies by Monte Carlo simulations, including all lensing effects such as magnification, distortion, and multiplication of images as well as detection completeness and contamination effects in a self-consistent manner. We find that UV luminosity functions at z∼ 6{--}8 have steep faint-end slopes, α ∼ -2, and likely steeper slopes, α ≲ -2 at z∼ 9{--}10. We also find that the evolution of UV luminosity densities shows a non-accelerated decline beyond z∼ 8 in the case of {M}trunc}=-15, but an accelerated one in the case of {M}trunc}=-17. We examine whether our results are consistent with the Thomson scattering optical depth from the Planck satellite and the ionized hydrogen fraction Q H II at z≲ 7 based on the standard analytic reionization model. We find that reionization scenarios exist that consistently explain all of the observational measurements with the allowed parameters of {f}esc}={0.17}-0.03+0.07 and {M}trunc}> -14.0 for {log}{ξ }ion}/[{erg}}-1 {Hz}]=25.34, where {f}esc} is the escape fraction, M trunc is the faint limit of the UV luminosity function, and {ξ }ion} is the conversion factor of the UV luminosity to the ionizing photon emission rate. The length of the reionization period is estimated to be {{Δ }}z={3.9}-1.6+2.0 (for 0.1< {Q}{{H}{{II}}}< 0.99), consistent with the recent estimate from Planck.

No difference in long-term trunk muscle strength, cross-sectional area, and density in patients with chronic low back pain 7 to 11 years after lumbar fusion versus cognitive intervention and exercises.

PubMed

Froholdt, Anne; Holm, Inger; Keller, Anne; Gunderson, Ragnhild B; Reikeraas, Olav; Brox, Jens I

2011-08-01

Reduced muscle strength and density observed at 1 year after lumbar fusion may deteriorate more in the long term. To compare the long-term effect of lumbar fusion and cognitive intervention and exercises on muscle strength, cross-sectional area, density, and self-rated function in patients with chronic low back pain (CLBP) and disc degeneration. Randomized controlled study with a follow-up examination at 8.5 years (range, 7-11 years). Patients with CLBP and disc degeneration randomized to either instrumented posterolateral fusion of one or both of the two lower lumbar levels or a 3-week cognitive intervention and exercise program were included. Isokinetic muscle strength was measured by a Cybex 6000 (Cybex-Lumex, Inc., Ronkonkoma, NY, USA). All patients had previous experience with the test procedure. The back extension (E) flexion (F) muscles were tested, and the E/F ratios were calculated. Cross-sectional area and density of the back muscles were measured at the L3-L4 segment by computed tomography. Patients rated their function by the General Function Score. Trunk muscle strength, cross-sectional area, density, and self-rated function. Fifty-five patients (90%) were included at long-term follow-up. There were no significant differences in cross-sectional area, density, muscle strength, or self-rated function between the two groups. The cognitive intervention and exercise group increased trunk muscle extension significantly (p<.05), and both groups performed significantly better on trunk muscle flexion tests (p<.01) at long-term follow-up. On average, self-rated function improved by 56%, cross-sectional area was reduced by 8.5%, and muscle density was reduced by 27%. Although this study did not assess the morphology of muscles likely damaged by surgery, trunk muscle strength and cross-sectional area above the surgical levels are not different between those who had lumbar fusion or cognitive intervention and exercises at 7- to 11-year follow-up. Copyright © 2011 Elsevier Inc. All rights reserved.

Formation of the Electric Double Layer and its Effects on Moving Bodies in a Space Plasma Environment

NASA Technical Reports Server (NTRS)

Yang, Qianli; Wu, S. T.; Stone, N. H.; Li, Xiaoquing

1996-01-01

In this paper we solve the self-consistent Vlasov and Poisson equations by a numerical method to determine the local distribution function of the ion and the electron, within a thin layer near the moving body, respectively. Using these ion and electron distributions, the number density for the ions and electrons are determined, such that, the electric potential is obtained within this thin layer (i.e., measured by Debye length). Numerical results are presented for temporal evolution of the electron and ion density and its corresponding electric potential within the layer which shows the formation of electric double layer and its structures. From these numerical results, we are able to determine the maximum conditions of the electric potential, it may create satellite anomaly.

Electrostatic correlations in inhomogeneous charged fluids beyond loop expansion

NASA Astrophysics Data System (ADS)

Buyukdagli, Sahin; Achim, C. V.; Ala-Nissila, T.

2012-09-01

Electrostatic correlation effects in inhomogeneous symmetric electrolytes are investigated within a previously developed electrostatic self-consistent theory [R. R. Netz and H. Orland, Eur. Phys. J. E 11, 301 (2003)], 10.1140/epje/i2002-10159-0. To this aim, we introduce two computational approaches that allow to solve the self-consistent equations beyond the loop expansion. The first method is based on a perturbative Green's function technique, and the second one is an extension of a previously introduced semiclassical approximation for single dielectric interfaces to the case of slit nanopores. Both approaches can handle the case of dielectrically discontinuous boundaries where the one-loop theory is known to fail. By comparing the theoretical results obtained from these schemes with the results of the Monte Carlo simulations that we ran for ions at neutral single dielectric interfaces, we first show that the weak coupling Debye-Huckel theory remains quantitatively accurate up to the bulk ion density ρb ≃ 0.01 M, whereas the self-consistent theory exhibits a good quantitative accuracy up to ρb ≃ 0.2 M, thus improving the accuracy of the Debye-Huckel theory by one order of magnitude in ionic strength. Furthermore, we compare the predictions of the self-consistent theory with previous Monte Carlo simulation data for charged dielectric interfaces and show that the proposed approaches can also accurately handle the correlation effects induced by the surface charge in a parameter regime where the mean-field result significantly deviates from the Monte Carlo data. Then, we derive from the perturbative self-consistent scheme the one-loop theory of asymmetrically partitioned salt systems around a dielectrically homogeneous charged surface. It is shown that correlation effects originate in these systems from a competition between the salt screening loss at the interface driving the ions to the bulk region, and the interfacial counterion screening excess attracting them towards the surface. This competition can be quantified in terms of the characteristic surface charge σ _s^*=√{2ρ _b/(π ℓ _B)}, where ℓB = 7 Å is the Bjerrum length. In the case of weak surface charges σ _s≪ σ _s^* where counterions form a diffuse layer, the interfacial salt screening loss is the dominant effect. As a result, correlation effects decrease the mean-field density of both coions and counterions. With an increase of the surface charge towards σ _s^*, the surface-attractive counterion screening excess starts to dominate, and correlation effects amplify in this regime the mean-field density of both type of ions. However, in the regime σ _s>σ _s^*, the same counterion screening excess also results in a significant decrease of the electrostatic mean-field potential. This reduces in turn the mean-field counterion density far from the charged surface. We also show that for σ _s≫ σ _s^*, electrostatic correlations result in a charge inversion effect. However, the electrostatic coupling regime where this phenomenon takes place should be verified with Monte Carlo simulations since this parameter regime is located beyond the validity range of the one-loop theory.

Electrostatic correlations in inhomogeneous charged fluids beyond loop expansion.

PubMed

Buyukdagli, Sahin; Achim, C V; Ala-Nissila, T

2012-09-14

Electrostatic correlation effects in inhomogeneous symmetric electrolytes are investigated within a previously developed electrostatic self-consistent theory [R. R. Netz and H. Orland, Eur. Phys. J. E 11, 301 (2003)]. To this aim, we introduce two computational approaches that allow to solve the self-consistent equations beyond the loop expansion. The first method is based on a perturbative Green's function technique, and the second one is an extension of a previously introduced semiclassical approximation for single dielectric interfaces to the case of slit nanopores. Both approaches can handle the case of dielectrically discontinuous boundaries where the one-loop theory is known to fail. By comparing the theoretical results obtained from these schemes with the results of the Monte Carlo simulations that we ran for ions at neutral single dielectric interfaces, we first show that the weak coupling Debye-Huckel theory remains quantitatively accurate up to the bulk ion density ρ(b) ≃ 0.01 M, whereas the self-consistent theory exhibits a good quantitative accuracy up to ρ(b) ≃ 0.2 M, thus improving the accuracy of the Debye-Huckel theory by one order of magnitude in ionic strength. Furthermore, we compare the predictions of the self-consistent theory with previous Monte Carlo simulation data for charged dielectric interfaces and show that the proposed approaches can also accurately handle the correlation effects induced by the surface charge in a parameter regime where the mean-field result significantly deviates from the Monte Carlo data. Then, we derive from the perturbative self-consistent scheme the one-loop theory of asymmetrically partitioned salt systems around a dielectrically homogeneous charged surface. It is shown that correlation effects originate in these systems from a competition between the salt screening loss at the interface driving the ions to the bulk region, and the interfacial counterion screening excess attracting them towards the surface. This competition can be quantified in terms of the characteristic surface charge σ(s)*=√(2ρ(b)/(πl(B)), where l(B) = 7 Å is the Bjerrum length. In the case of weak surface charges σ(s)≪σ(s)* where counterions form a diffuse layer, the interfacial salt screening loss is the dominant effect. As a result, correlation effects decrease the mean-field density of both coions and counterions. With an increase of the surface charge towards σ(s)*, the surface-attractive counterion screening excess starts to dominate, and correlation effects amplify in this regime the mean-field density of both type of ions. However, in the regime σ(s)>σ(s)*, the same counterion screening excess also results in a significant decrease of the electrostatic mean-field potential. This reduces in turn the mean-field counterion density far from the charged surface. We also show that for σ(s)≫σ(s)*, electrostatic correlations result in a charge inversion effect. However, the electrostatic coupling regime where this phenomenon takes place should be verified with Monte Carlo simulations since this parameter regime is located beyond the validity range of the one-loop theory.

Modified free volume theory of self-diffusion and molecular theory of shear viscosity of liquid carbon dioxide.

PubMed

Nasrabad, Afshin Eskandari; Laghaei, Rozita; Eu, Byung Chan

2005-04-28

In previous work on the density fluctuation theory of transport coefficients of liquids, it was necessary to use empirical self-diffusion coefficients to calculate the transport coefficients (e.g., shear viscosity of carbon dioxide). In this work, the necessity of empirical input of the self-diffusion coefficients in the calculation of shear viscosity is removed, and the theory is thus made a self-contained molecular theory of transport coefficients of liquids, albeit it contains an empirical parameter in the subcritical regime. The required self-diffusion coefficients of liquid carbon dioxide are calculated by using the modified free volume theory for which the generic van der Waals equation of state and Monte Carlo simulations are combined to accurately compute the mean free volume by means of statistical mechanics. They have been computed as a function of density along four different isotherms and isobars. A Lennard-Jones site-site interaction potential was used to model the molecular carbon dioxide interaction. The density and temperature dependence of the theoretical self-diffusion coefficients are shown to be in excellent agreement with experimental data when the minimum critical free volume is identified with the molecular volume. The self-diffusion coefficients thus computed are then used to compute the density and temperature dependence of the shear viscosity of liquid carbon dioxide by employing the density fluctuation theory formula for shear viscosity as reported in an earlier paper (J. Chem. Phys. 2000, 112, 7118). The theoretical shear viscosity is shown to be robust and yields excellent density and temperature dependence for carbon dioxide. The pair correlation function appearing in the theory has been computed by Monte Carlo simulations.

On a self-consistent representation of earth models, with an application to the computing of internal flattening

NASA Astrophysics Data System (ADS)

Denis, C.; Ibrahim, A.

Self-consistent parametric earth models are discussed in terms of a flexible numerical code. The density profile of each layer is represented as a polynomial, and figures of gravity, mass, mean density, hydrostatic pressure, and moment of inertia are derived. The polynomial representation also allows computation of the first order flattening of the internal strata of some models, using a Gauss-Legendre quadrature with a rapidly converging iteration technique. Agreement with measured geophysical data is obtained, and algorithm for estimation of the geometric flattening for any equidense surface identified by its fractional radius is developed. The program can also be applied in studies of planetary and stellar models.

Generalized non-equilibrium vertex correction method in coherent medium theory for quantum transport simulation of disordered nanoelectronics

NASA Astrophysics Data System (ADS)

Yan, Jiawei; Ke, Youqi

In realistic nanoelectronics, disordered impurities/defects are inevitable and play important roles in electron transport. However, due to the lack of effective quantum transport method, the important effects of disorders remain poorly understood. Here, we report a generalized non-equilibrium vertex correction (NVC) method with coherent potential approximation to treat the disorder effects in quantum transport simulation. With this generalized NVC method, any averaged product of two single-particle Green's functions can be obtained by solving a set of simple linear equations. As a result, the averaged non-equilibrium density matrix and various important transport properties, including averaged current, disordered induced current fluctuation and the averaged shot noise, can all be efficiently computed in a unified scheme. Moreover, a generalized form of conditionally averaged non-equilibrium Green's function is derived to incorporate with density functional theory to enable first-principles simulation. We prove the non-equilibrium coherent potential equals the non-equilibrium vertex correction. Our approach provides a unified, efficient and self-consistent method for simulating non-equilibrium quantum transport through disorder nanoelectronics. Shanghaitech start-up fund.

The heat of formation of gaseous PuO(2)2+ from relativistic density functional calculations.

PubMed

Moskaleva, Lyudmila V; Matveev, Alexei V; Dengler, Joachim; Rösch, Notker

2006-08-28

Using a set of model reactions, we estimated the heat of formation of gaseous PuO2(2+) from quantum-chemical reaction enthalpies and experimental heats of formation of reference species. To this end, we carried out relativistic density functional calculations on the molecules PuO(2)2+, PuO2, PuF6, and PuF4. We used a revised variant (PBEN) of the Perdew-Burke-Ernzerhof gradient-corrected exchange-correlation functional, and we accounted for spin-orbit interaction in a self-consistent fashion. As open-shell Pu species with two or more unpaired 5f electrons are involved, spin-orbit interaction significantly affects the energies of the model reactions. Our theoretical estimate for the heat of formation DeltafH degree 0(PuO2(2+),g), 418+/-15 kcal mol-1, evaluated using plutonium fluorides as references, is in good agreement with a recent experimental result, 413+/-16 kcal mol-1. The theoretical value connected to the experimental heat of formation of PuO2(g) has a notably higher uncertainty and therefore was not included in the final result.

New Evidence for a Large Local Void From the UKIDSS LAS + SDSS

NASA Astrophysics Data System (ADS)

Keenan, Ryan; Barger, A. J.

2013-01-01

Recent cosmological modeling efforts have shown that a local under-density on scales of a few hundred Mpc (out to z ~ 0.1) could produce the apparent acceleration of the expansion of the universe observed via type Ia supernovae. Several studies of galaxy counts in the near-infrared (NIR) have found that the local universe appears underdense by ~25 - 50% compared with regions a few hundred Mpc distant (e.g. Keenan et al., 2010). An accurate characterization of any such under-density will be important for studies seeking to understand the nature of dark energy. If the space density of galaxies is rising as a function of redshift, then the luminosity density, as measured via the NIR galaxy luminosity function (LF), should be rising as well. In Keenan et al. (2012), we presented a study of the NIR LF at z ~ 0.2 and found that the product φ*L* (the peak of the luminosity density distribution) at z ~ 0.2 is roughly ~ 30% higher than that measured at z ~ 0.05. Here we present the results from a study of the NIR LF derived from galaxies selected from the UKIRT Infrared Deep Sky Large Area Survey (UKIDSS LAS) combined with spectroscopy from the Sloan Digital Sky Survey (SDSS). We confirm the apparent rise in luminosity density found in Keenan et al. (2012) from z = 0.05 to z = 0.1 and provide the first self-consistent measurements of the NIR luminosity density out to z ~ 0.15.

Density-Functional Theory with Optimized Effective Potential and Self-Interaction Correction for the Double Ionization of He and Be Atoms

NASA Astrophysics Data System (ADS)

Heslar, John; Telnov, Dmitry; Chu, Shih-I.

2012-06-01

We present a self-interaction-free (SIC) time-dependent density-functional theory (TDDFT) for the treatment of double ionization processes of many-electron systems. The method is based on the Krieger-Li-Iafrate (KLI) treatment of the optimized effective potential (OEP) theory and the incorporation of an explicit self-interaction correction (SIC) term. In the framework of the time-dependent density functional theory, we have performed 3D calculations of double ionization of He and Be atoms by strong near-infrared laser fields. We make use of the exchange-correlation potential with the integer discontinuity which improves the description of the double ionization process. We found that proper description of the double ionization requires the TDDFT exchange-correlation potential with the discontinuity with respect to the variation of the spin particle numbers (SPN) only. The results for the intensity-dependent probabilities of single and double ionization are presented and reproduce the famous ``knee'' structure.

Surface properties of neutron-rich exotic nuclei within relativistic mean field formalisms

NASA Astrophysics Data System (ADS)

Bhuyan, M.; Carlson, B. V.; Patra, S. K.; Zhou, Shan-Gui

2018-02-01

In this theoretical study, we establish a correlation between the neutron skin thickness and the nuclear symmetry energy for the even-even isotopes of Fe, Ni, Zn, Ge, Se, and Kr within the framework of the axially deformed self-consistent relativistic mean field for the nonlinear NL 3* and density-dependent DD-ME1 interactions. The coherent density functional method is used to formulate the symmetry energy, the neutron pressure, and the curvature of finite nuclei as a function of the nuclear radius. We have performed broad studies for the mass dependence on the symmetry energy in terms of the neutron-proton asymmetry for mass 70 ≤A ≤96 . From this analysis, we found a notable signature of a shell closure at N =50 in the isotopic chains of Fe, Ni, Zn, Ge, Se, and Kr nuclei. The present study reveals a interrelationship between the characteristics of infinite nuclear matter and the neutron skin thickness of finite nuclei.

Scalable real space pseudopotential density functional codes for materials in the exascale regime

NASA Astrophysics Data System (ADS)

Lena, Charles; Chelikowsky, James; Schofield, Grady; Biller, Ariel; Kronik, Leeor; Saad, Yousef; Deslippe, Jack

Real-space pseudopotential density functional theory has proven to be an efficient method for computing the properties of matter in many different states and geometries, including liquids, wires, slabs, and clusters with and without spin polarization. Fully self-consistent solutions using this approach have been routinely obtained for systems with thousands of atoms. Yet, there are many systems of notable larger sizes where quantum mechanical accuracy is desired, but scalability proves to be a hindrance. Such systems include large biological molecules, complex nanostructures, or mismatched interfaces. We will present an overview of our new massively parallel algorithms, which offer improved scalability in preparation for exascale supercomputing. We will illustrate these algorithms by considering the electronic structure of a Si nanocrystal exceeding 104 atoms. Support provided by the SciDAC program, Department of Energy, Office of Science, Advanced Scientific Computing Research and Basic Energy Sciences. Grant Numbers DE-SC0008877 (Austin) and DE-FG02-12ER4 (Berkeley).

Subgap in the Surface Bound States Spectrum of Superfluid (3) 3 He-B with Rough Surface

NASA Astrophysics Data System (ADS)

Nagato, Y.; Higashitani, S.; Nagai, K.

2018-03-01

The subgap structure in the surface bound states spectrum of superfluid ^3He-B with rough surface is discussed. The subgap is formed by the level repulsion between the surface bound state and the continuum states in the course of multiple scattering by the surface roughness. We show that the level repulsion is originated from the nature of the wave function of the surface bound state that is now recognized as Majorana fermion. We study the superfluid ^3He-B with a rough surface and in a magnetic field perpendicular to the surface using the quasi-classical Green function together with a random S-matrix model. We calculate the self-consistent order parameters, the spin polarization density and the surface density of states. It is shown that the subgap is found also in a magnetic field perpendicular to the surface. The magnetic field dependence of the transverse acoustic impedance is also discussed.

Are CO Observations of Interstellar Clouds Tracing the H2?

NASA Astrophysics Data System (ADS)

Federrath, Christoph; Glover, S. C. O.; Klessen, R. S.; Mac Low, M.

2010-01-01

Interstellar clouds are commonly observed through the emission of rotational transitions from carbon monoxide (CO). However, the abundance ratio of CO to molecular hydrogen (H2), which is the most abundant molecule in molecular clouds is only about 10-4. This raises the important question of whether the observed CO emission is actually tracing the bulk of the gas in these clouds, and whether it can be used to derive quantities like the total mass of the cloud, the gas density distribution function, the fractal dimension, and the velocity dispersion--size relation. To evaluate the usability and accuracy of CO as a tracer for H2 gas, we generate synthetic observations of hydrodynamical models that include a detailed chemical network to follow the formation and photo-dissociation of H2 and CO. These three-dimensional models of turbulent interstellar cloud formation self-consistently follow the coupled thermal, dynamical and chemical evolution of 32 species, with a particular focus on H2 and CO (Glover et al. 2009). We find that CO primarily traces the dense gas in the clouds, however, with a significant scatter due to turbulent mixing and self-shielding of H2 and CO. The H2 probability distribution function (PDF) is well-described by a log-normal distribution. In contrast, the CO column density PDF has a strongly non-Gaussian low-density wing, not at all consistent with a log-normal distribution. Centroid velocity statistics show that CO is more intermittent than H2, leading to an overestimate of the velocity scaling exponent in the velocity dispersion--size relation. With our systematic comparison of H2 and CO data from the numerical models, we hope to provide a statistical formula to correct for the bias of CO observations. CF acknowledges financial support from a Kade Fellowship of the American Museum of Natural History.

Self-consistent mapping of the ab initio calculations to the multi-orbital p- d model: Magnetism in α-FeSi2 films as the effect of the local environment

NASA Astrophysics Data System (ADS)

Zhandun, V.; Zamkova, N.; Ovchinnikov, S.; Sandalov, I.

2017-11-01

To accurately translate the results obtained within density functional theory (DFT) to the language of many-body theory we suggest and test the following approach: the parameters of the formulated model are to be found from the requirement that the model self-consistent electron density and density of electron states are as close as possible to the ones found from the DFT-based calculations. The investigation of the phase diagram of the model allows us to find the critical regions in magnetic properties. Then the behavior of the real system in these regions is checked by the ab initio calculations. As an example, we studied the physics of magnetic moment (MM) formation due to substitutions of Si by Fe-atoms or vice versa in the otherwise non-magnetic alloy α-FeSi2. We find that the MM formation is essentially controlled by the interaction of Fe atoms with its next nearest atoms (NNN) and by their particular arrangement. The latter may result in different magnetic states at the same concentrations of constituents. Moreover, one of arrangements produces the counterintuitive result: a ferromagnetism arises due to an increase in Si concentration in Fe1-xSi2+ x ordered alloy. The existing phenomenological models associate the destruction of magnetic moment only with the number of Fe-Si nearest neighbors. The presented results show that the crucial role in MM formation is played by the particular local NNN environment of the metal atom in the transition metal-metalloid alloy.

Self-crowding of AMPA receptors in the excitatory postsynaptic density can effectuate anomalous receptor sub-diffusion

PubMed Central

Gupta, Rahul

2018-01-01

AMPA receptors (AMPARs) and their associations with auxiliary transmembrane proteins are bulky structures with large steric-exclusion volumes. Hence, self-crowding of AMPARs, depending on the local density, may affect their lateral diffusion in the postsynaptic membrane as well as in the highly crowded postsynaptic density (PSD) at excitatory synapses. Earlier theoretical studies considered only the roles of transmembrane obstacles and the AMPAR-binding submembranous scaffold proteins in shaping receptor diffusion within PSD. Using lattice model of diffusion, the present study investigates the additional impacts of self-crowding on the anomalousity and effective diffusion coefficient (Deff) of AMPAR diffusion. A recursive algorithm for avoiding false self-blocking during diffusion simulation is also proposed. The findings suggest that high density of AMPARs in the obstacle-free membrane itself engenders strongly anomalous diffusion and severe decline in Deff. Adding transmembrane obstacles to the membrane accentuates the anomalousity arising from self-crowding due to the reduced free diffusion space. Contrarily, enhanced AMPAR-scaffold binding, either through increase in binding strength or scaffold density or both, ameliorates the anomalousity resulting from self-crowding. However, binding has differential impacts on Deff depending on the receptor density. Increase in binding causes consistent decrease in Deff for low and moderate receptor density. For high density, binding increases Deff as long as it reduces anomalousity associated with intense self-crowding. Given a sufficiently strong binding condition when diffusion acquires normal behavior, further increase in binding causes decrease in Deff. Supporting earlier experimental observations are mentioned and implications of present findings to the experimental observations on AMPAR diffusion are also drawn. PMID:29444074

Generalized extended Lagrangian Born-Oppenheimer molecular dynamics

DOE PAGES

Niklasson, Anders M. N.; Cawkwell, Marc J.

2014-10-29

Extended Lagrangian Born-Oppenheimer molecular dynamics based on Kohn-Sham density functional theory is generalized in the limit of vanishing self-consistent field optimization prior to the force evaluations. The equations of motion are derived directly from the extended Lagrangian under the condition of an adiabatic separation between the nuclear and the electronic degrees of freedom. We show how this separation is automatically fulfilled and system independent. The generalized equations of motion require only one diagonalization per time step and are applicable to a broader range of materials with improved accuracy and stability compared to previous formulations.

Multiple Chirality in Nuclear Rotation: A Microscopic View

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, P. W.

Covariant density functional theory and three-dimensional tilted axis cranking are used to investigate multiple chirality in nuclear rotation for the first time in a fully self-consistent and microscopic way. Two distinct sets of chiral solutions with negative and positive parities, respectively, are found in the nucleus 106Rh. The negative-parity solutions reproduce well the corresponding experimental spectrum as well as the B(M1)/B(E2) ratios of the transition strengths. Finally, this indicates that a predicted positive-parity chiral band should also exist. Therefore, it provides a further strong hint that multiple chirality is realized in nuclei.

Emulsifier-free emulsion polymerization produces highly charged, monodisperse particles for near infrared photonic crystals.

PubMed

Reese, Chad E; Asher, Sanford A

2002-04-01

We have developed emulsifier-free, emulsion polymerization recipes for the synthesis of highly charged, monodisperse latex particles of diameters between 500 and 1100 nm. These latexes consist of poly[styrene-(co-2-hydroxyethyl methacrylate)] spherical particles whose surfaces are functionalized with sulfate and carboxylic acid groups. These highly charged, monodisperse particles readily self-assemble into robust, three-dimensionally ordered crystalline colloidal array photonic crystals that Bragg diffract light in the near infrared spectral region. By altering the particle number density, the diffraction wavelength can be tuned from approximately 1000 to approximately 4000 nm.

Multiple Chirality in Nuclear Rotation: A Microscopic View

DOE PAGES

Zhao, P. W.

2017-10-10

Covariant density functional theory and three-dimensional tilted axis cranking are used to investigate multiple chirality in nuclear rotation for the first time in a fully self-consistent and microscopic way. Two distinct sets of chiral solutions with negative and positive parities, respectively, are found in the nucleus 106Rh. The negative-parity solutions reproduce well the corresponding experimental spectrum as well as the B(M1)/B(E2) ratios of the transition strengths. Finally, this indicates that a predicted positive-parity chiral band should also exist. Therefore, it provides a further strong hint that multiple chirality is realized in nuclei.

Electronic and structural properties of Lu under pressure: Relation to structural phases of the rare-earth metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Min, B.I.; Oguchi, T.; Jansen, H.J.F.

1986-07-15

Ground-state electronic and structural properties of Lu under pressure are investigated with use of the self-consistent all-electron total-energy linear muffin-tin orbital band-structure method within a local-density-functional approximation. Pressure-induced structural transitions are found to occur in the following sequence: hcp--(Sm-type)--dhcp--fcc, which is the same as that observed in the crystal structures of the trivalent rare-earth metals with decreasing atomic number. This structural transition is correlated with the increase in the number of d-italic electrons under pressure.

Frictional response of fatty acids on steel.

PubMed

Sahoo, Rashmi R; Biswas, S K

2009-05-15

Self-assembled monolayers of fatty acids were formed on stainless steel by room-temperature solution deposition. The acids are covalently bound to the surface as carboxylate in a bidentate manner. To explore the effect of saturation in the carbon backbone on friction in sliding tribology, we study the response of saturated stearic acid (SA) and unsaturated linoleic acid (LA) as self-assembled monolayers using lateral force microscopy and nanotribometry and when the molecules are dispersed in hexadecane, using pin-on-disc tribometry. Over a very wide range (10 MPa-2.5 GPa) of contact pressures it is consistently demonstrated that the unsaturated linoleic acid molecules yield friction which is significantly lower than that of the saturated stearic acid. It is argued, using density functional theory predictions and XPS of slid track, that when the molecular backbone of unsaturated fatty acids are tilted and pressed strongly by a probe, in tribological contact, the high charge density of the double bond region of the backbone allows coupling with the steel substrate. The interaction yields a low friction carboxylate soap film on the substrate. The saturated fatty acid does not show this effect.

Self-consistent models for Coulomb heated X-ray pulsar atmospheres

NASA Technical Reports Server (NTRS)

Harding, A.; Meszaros, S. P.; Kirk, J.; Galloway, D.

1983-01-01

Calculations of accreting magnetized neutron star atmospheres heated by the gradual deceleration of protons via Coulomb collisions are presented. Self consistent determinations of the temperature and density structure for different accretion rates are made by assuming hydrostatic equilibrium and energy balance, coupled with radiative transfer. The full radiative transfer in two polarizations, using magnetic cross sections but with cyclotron resonance effects treated approximately, is carried out in the inhomogeneous atmospheres.

Monolithically Integrated Self-Charging Power Pack Consisting of a Silicon Nanowire Array/Conductive Polymer Hybrid Solar Cell and a Laser-Scribed Graphene Supercapacitor.

PubMed

Liu, Hanhui; Li, Mengping; Kaner, Richard B; Chen, Songyan; Pei, Qibing

2018-05-09

Owing to the need for portable and sustainable energy sources and the development trend for microminiaturization and multifunctionalization in the electronic components, the study of integrated self-charging power packs has attracted increasing attention. A new self-charging power pack consisting of a silicon nanowire array/poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) hybrid solar cell and a laser-scribed graphene (LSG) supercapacitor has been fabricated. The Si nanowire array/PEDOT:PSS hybrid solar cell structure exhibited a high power conversion efficiency (PCE) of 12.37%. The LSG demonstrated excellent energy storage capability for the power pack, with high current density, energy density, and cyclic stability when compared to other supercapacitor electrodes such as active carbon and conducting polymers. The overall efficiency of the power unit is 2.92%.

Design principles for radiation-resistant solid solutions

NASA Astrophysics Data System (ADS)

Schuler, Thomas; Trinkle, Dallas R.; Bellon, Pascal; Averback, Robert

2017-05-01

We develop a multiscale approach to quantify the increase in the recombined fraction of point defects under irradiation resulting from dilute solute additions to a solid solution. This methodology provides design principles for radiation-resistant materials. Using an existing database of solute diffusivities, we identify Sb as one of the most efficient solutes for this purpose in a Cu matrix. We perform density-functional-theory calculations to obtain binding and migration energies of Sb atoms, vacancies, and self-interstitial atoms in various configurations. The computed data informs the self-consistent mean-field formalism to calculate transport coefficients, allowing us to make quantitative predictions of the recombined fraction of point defects as a function of temperature and irradiation rate using homogeneous rate equations. We identify two different mechanisms according to which solutes lead to an increase in the recombined fraction of point defects; at low temperature, solutes slow down vacancies (kinetic effect), while at high temperature, solutes stabilize vacancies in the solid solution (thermodynamic effect). Extension to other metallic matrices and solutes are discussed.

DGDFT: A massively parallel method for large scale density functional theory calculations.

PubMed

Hu, Wei; Lin, Lin; Yang, Chao

2015-09-28

We describe a massively parallel implementation of the recently developed discontinuous Galerkin density functional theory (DGDFT) method, for efficient large-scale Kohn-Sham DFT based electronic structure calculations. The DGDFT method uses adaptive local basis (ALB) functions generated on-the-fly during the self-consistent field iteration to represent the solution to the Kohn-Sham equations. The use of the ALB set provides a systematic way to improve the accuracy of the approximation. By using the pole expansion and selected inversion technique to compute electron density, energy, and atomic forces, we can make the computational complexity of DGDFT scale at most quadratically with respect to the number of electrons for both insulating and metallic systems. We show that for the two-dimensional (2D) phosphorene systems studied here, using 37 basis functions per atom allows us to reach an accuracy level of 1.3 × 10(-4) Hartree/atom in terms of the error of energy and 6.2 × 10(-4) Hartree/bohr in terms of the error of atomic force, respectively. DGDFT can achieve 80% parallel efficiency on 128,000 high performance computing cores when it is used to study the electronic structure of 2D phosphorene systems with 3500-14 000 atoms. This high parallel efficiency results from a two-level parallelization scheme that we will describe in detail.

Edge reconstruction in armchair phosphorene nanoribbons revealed by discontinuous Galerkin density functional theory.

PubMed

Hu, Wei; Lin, Lin; Yang, Chao

2015-12-21

With the help of our recently developed massively parallel DGDFT (Discontinuous Galerkin Density Functional Theory) methodology, we perform large-scale Kohn-Sham density functional theory calculations on phosphorene nanoribbons with armchair edges (ACPNRs) containing a few thousands to ten thousand atoms. The use of DGDFT allows us to systematically achieve a conventional plane wave basis set type of accuracy, but with a much smaller number (about 15) of adaptive local basis (ALB) functions per atom for this system. The relatively small number of degrees of freedom required to represent the Kohn-Sham Hamiltonian, together with the use of the pole expansion the selected inversion (PEXSI) technique that circumvents the need to diagonalize the Hamiltonian, results in a highly efficient and scalable computational scheme for analyzing the electronic structures of ACPNRs as well as their dynamics. The total wall clock time for calculating the electronic structures of large-scale ACPNRs containing 1080-10,800 atoms is only 10-25 s per self-consistent field (SCF) iteration, with accuracy fully comparable to that obtained from conventional planewave DFT calculations. For the ACPNR system, we observe that the DGDFT methodology can scale to 5000-50,000 processors. We use DGDFT based ab initio molecular dynamics (AIMD) calculations to study the thermodynamic stability of ACPNRs. Our calculations reveal that a 2 × 1 edge reconstruction appears in ACPNRs at room temperature.

The optimized effective potential and the self-interaction correction in density functional theory: Application to molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garza, Jorge; Nichols, Jeffrey A.; Dixon, David A.

2000-05-08

The Krieger, Li, and Iafrate approximation to the optimized effective potential including the self-interaction correction for density functional theory has been implemented in a molecular code, NWChem, that uses Gaussian functions to represent the Kohn and Sham spin-orbitals. The differences between the implementation of the self-interaction correction in codes where planewaves are used with an optimized effective potential are discussed. The importance of the localization of the spin-orbitals to maximize the exchange-correlation of the self-interaction correction is discussed. We carried out exchange-only calculations to compare the results obtained with these approximations, and those obtained with the local spin density approximation,more » the generalized gradient approximation and Hartree-Fock theory. Interesting results for the energy difference (GAP) between the highest occupied molecular orbital, HOMO, and the lowest unoccupied molecular orbital, LUMO, (spin-orbital energies of closed shell atoms and molecules) using the optimized effective potential and the self-interaction correction have been obtained. The effect of the diffuse character of the basis set on the HOMO and LUMO eigenvalues at the various levels is discussed. Total energies obtained with the optimized effective potential and the self-interaction correction show that the exchange energy with these approximations is overestimated and this will be an important topic for future work. (c) 2000 American Institute of Physics.« less

Local-spin-density calculations for iron: Effect of spin interpolation on ground-state properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacLaren, J.M.; Clougherty, D.P.; Albers, R.C.

1990-08-15

Scalar-relativistic self-consistent linear muffin-tin orbital (LMTO) calculations for bcc and fcc Fe have been performed with several different local approximations to the exchange and correlation energy density and potential. Overall, in contrast to the conclusions of previous studies, we find that the local-spin-density approximation to exchange and correlation can provide an adequate description of bulk Fe {ital provided} that a proper parametrization of the correlation energy density and potential of the homogeneous electron gas over both spin and density is used. Lattice constants, found from the position of the minimum of the total energy as a function of Wigner-Seitz radius,more » agree to within 1% (for {ital s},{ital p},{ital d} LMTO's only) and within 1--2% (for {ital s},{ital p},{ital d},{ital f} LMTO's) of the experimental lattice constants for all forms used for the local correlation. The best agreement, however, was obtained using a local correlation potential derived from the Vosko-Wilk-Nusair form for the spin dependence of the correlation energy density. The calculation performed with this correlation potential was also the only calculation to correctly predict a bcc ferromagnetic ground state.« less

Excitation energies of molecules within time-independent density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hemanadhan, M., E-mail: hemanadh@iitk.ac.in; Harbola, Manoj K., E-mail: hemanadh@iitk.ac.in

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.

Excitation energies of molecules within time-independent density functional theory

NASA Astrophysics Data System (ADS)

Hemanadhan, M.; Harbola, Manoj K.

2014-04-01

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 N2 and CO diatomic molecules. The excitation energy obtained with the MLSD functional for the N2 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.

An ab initio CASSCF study of zero field splitting fluctuations in the octet ground state of aqueous [Gd(iii)(HPDO3A)(H2O)

NASA Astrophysics Data System (ADS)

Khan, Shehryar; Pollet, Rodolphe; Vuilleumier, Rodolphe; Kowalewski, Jozef; Odelius, Michael

2017-12-01

In this work, we present ab initio calculations of the zero-field splitting (ZFS) of a gadolinium complex [Gd(iii)(HPDO3A)(H2O)] sampled from an ab initio molecular dynamics (AIMD) simulation. We perform both post-Hartree-Fock (complete active space self-consistent field—CASSCF) and density functional theory (DFT) calculations of the ZFS and compare and contrast the methods with experimental data. Two different density functional approximations (TPSS and LC-BLYP) were investigated. The magnitude of the ZFS from the CASSCF calculations is in good agreement with experiment, whereas the DFT results in varying degrees overestimate the magnitude of the ZFS for both functionals and exhibit a strong functional dependence. It was found in the sampling over the AIMD trajectory that the fluctuations in the transient ZFS tensor derived from DFT are not correlated with those of CASSCF nor does the magnitude of the ZFS from CASSCF and DFT correlate. From the fluctuations in the ZFS tensor, we extract a correlation time of the transient ZFS which is on the sub-picosecond time scale, showing a faster decay than experimental estimates.

Convergence of quasiparticle self-consistent G W calculations of transition-metal monoxides

NASA Astrophysics Data System (ADS)

Das, Suvadip; Coulter, John E.; Manousakis, Efstratios

2015-03-01

Finding an accurate ab initio approach for calculating the electronic properties of transition-metal oxides has been a problem for several decades. In this paper, we investigate the electronic structure of the transition-metal monoxides MnO, CoO, and NiO in their undistorted rocksalt structure within a fully iterated quasiparticle self-consistent G W (QPsc G W ) scheme. We study the convergence of the QPsc G W method, i.e., how the quasiparticle energy eigenvalues and wave functions converge as a function of the QPsc G W iterations, and we compare the converged outputs obtained from different starting wave functions. We find that the convergence is slow and that a one-shot G0W0 calculation does not significantly improve the initial eigenvalues and states. It is important to notice that in some cases the "path" to convergence may go through energy band reordering which cannot be captured by the simple initial unperturbed Hamiltonian. When we reach a fully iterated solution, the converged density of states, band gaps, and magnetic moments of these oxides are found to be only weakly dependent on the choice of the starting wave functions and in reasonably good agreement with the experiment. Finally, this approach provides a clear picture of the interplay between the various orbitals near the Fermi level of these simple transition-metal monoxides. The results of these accurate ab initio calculations can provide input for models aiming at describing the low-energy physics in these materials.

Soliton matter in the two-dimensional linear sigma model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dodd, L.R.; Lohe, M.A.; Rossi, M.

1987-10-01

We consider a one-dimensional model of nuclear matter where the quark clusters are described by solutions of the sigma model on a linear lattice in the self-consistent mean field approximation. Exact expressions are given for the baglike solutions confined to a finite interval, corresponding in the infinite interval limit to the free solitons previously found by Campbell and Liao. Periodic, self-consistent solutions which satisfy Bloch's theorem are constructed. Their energies and associated quark sigma field distributions are calculated numerically as functions of the baryon spacing, and compared with those of the uniform quark plasma. The predicted configuration of the groundmore » state depends critically on the assumed manner of filling the lowest band of quark single-particle levels, and on the density. In the absence of additional repulsive forces in the model, we find that the high density massless quark plasma is energetically favored and that there is a smooth transition from the baglike state to a uniform plasma with nonvanishing sigma field at comparatively large lattice constants 2dapprox. =10m/sub q//sup -1/ (m/sub q/ is the quark mass). If dilute filling of the entire band is employed, the clustered state is stable and a first order phase transition can occur for a range of much smaller lattice spacings 2dapprox. =4m/sub q//sup -1/. .AE« less

Self-interaction corrected LDA + U investigations of BiFeO3 properties: plane-wave pseudopotential method

NASA Astrophysics Data System (ADS)

Yaakob, M. K.; Taib, M. F. M.; Lu, L.; Hassan, O. H.; Yahya, M. Z. A.

2015-11-01

The structural, electronic, elastic, and optical properties of BiFeO3 were investigated using the first-principles calculation based on the local density approximation plus U (LDA + U) method in the frame of plane-wave pseudopotential density functional theory. The application of self-interaction corrected LDA + U method improved the accuracy of the calculated properties. Results of structural, electronic, elastic, and optical properties of BiFeO3, calculated using the LDA + U method were in good agreement with other calculation and experimental data; the optimized choice of on-site Coulomb repulsion U was 3 eV for the treatment of strong electronic localized Fe 3d electrons. Based on the calculated band structure and density of states, the on-site Coulomb repulsion U had a significant effect on the hybridized O 2p and Fe 3d states at the valence and the conduction band. Moreover, the elastic stiffness tensor, the longitudinal and shear wave velocities, bulk modulus, Poisson’s ratio, and the Debye temperature were calculated for U = 0, 3, and 6 eV. The elastic stiffness tensor, bulk modulus, sound velocities, and Debye temperature of BiFeO3 consistently decreased with the increase of the U value.

Simulations of material mixing in laser-driven reshock experiments

NASA Astrophysics Data System (ADS)

Haines, Brian M.; Grinstein, Fernando F.; Welser-Sherrill, Leslie; Fincke, James R.

2013-02-01

We perform simulations of a laser-driven reshock experiment [Welser-Sherrill et al., High Energy Density Phys. (unpublished)] in the strong-shock high energy-density regime to better understand material mixing driven by the Richtmyer-Meshkov instability. Validation of the simulations is based on direct comparison of simulation and radiographic data. Simulations are also compared with published direct numerical simulation and the theory of homogeneous isotropic turbulence. Despite the fact that the flow is neither homogeneous, isotropic nor fully turbulent, there are local regions in which the flow demonstrates characteristics of homogeneous isotropic turbulence. We identify and isolate these regions by the presence of high levels of turbulent kinetic energy (TKE) and vorticity. After reshock, our analysis shows characteristics consistent with those of incompressible isotropic turbulence. Self-similarity and effective Reynolds number assessments suggest that the results are reasonably converged at the finest resolution. Our results show that in shock-driven transitional flows, turbulent features such as self-similarity and isotropy only fully develop once de-correlation, characteristic vorticity distributions, and integrated TKE, have decayed significantly. Finally, we use three-dimensional simulation results to test the performance of two-dimensional Reynolds-averaged Navier-Stokes simulations. In this context, we also test a presumed probability density function turbulent mixing model extensively used in combustion applications.

Linearized self-consistent GW approach satisfying the Ward identity

NASA Astrophysics Data System (ADS)

Kuwahara, Riichi; Ohno, Kaoru

2014-09-01

We propose a linearized self-consistent GW approach satisfying the Ward identity. The vertex function derived from the Ward-Takahashi identity in the limit of q =0 and ω -ω'=0 is included in the self-energy and the polarization function as a consequence of the linearization of the quasiparticle equation. Due to the energy dependence of the self-energy, the Hamiltonian is a non-Hermitian operator and quasiparticle states are nonorthonormal and linearly dependent. However, the linearized quasiparticle states recover orthonormality and fulfill the completeness condition. This approach is very efficient, and the resulting quasiparticle energies are greatly improved compared to the nonlinearized self-consistent GW approach, although its computational cost is not much increased. We show the results for atoms and dimers of Li and Na compared with other approaches. We also propose convenient ways to calculate the Luttinger-Ward functional Φ based on a plasmon-pole model and calculate the total energy for the ground state. As a result, we conclude that the linearization improves overall behaviors in the self-consistent GW approach.

Two-Dimensional Self-Consistent Radio Frequency Plasma Simulations Relevant to the Gaseous Electronics Conference RF Reference Cell

PubMed Central

Lymberopoulos, Dimitris P.; Economou, Demetre J.

1995-01-01

Over the past few years multidimensional self-consistent plasma simulations including complex chemistry have been developed which are promising tools for furthering our understanding of reactive gas plasmas and for reactor design and optimization. These simulations must be benchmarked against experimental data obtained in well-characterized systems such as the Gaseous Electronics Conference (GEC) reference cell. Two-dimensional simulations relevant to the GEC Cell are reviewed in this paper with emphasis on fluid simulations. Important features observed experimentally, such as off-axis maxima in the charge density and hot spots of metastable species density near the electrode edges in capacitively-coupled GEC cells, have been captured by these simulations. PMID:29151756

Self-consistent adjoint analysis for topology optimization of electromagnetic waves

NASA Astrophysics Data System (ADS)

Deng, Yongbo; Korvink, Jan G.

2018-05-01

In topology optimization of electromagnetic waves, the Gâteaux differentiability of the conjugate operator to the complex field variable results in the complexity of the adjoint sensitivity, which evolves the original real-valued design variable to be complex during the iterative solution procedure. Therefore, the self-inconsistency of the adjoint sensitivity is presented. To enforce the self-consistency, the real part operator has been used to extract the real part of the sensitivity to keep the real-value property of the design variable. However, this enforced self-consistency can cause the problem that the derived structural topology has unreasonable dependence on the phase of the incident wave. To solve this problem, this article focuses on the self-consistent adjoint analysis of the topology optimization problems for electromagnetic waves. This self-consistent adjoint analysis is implemented by splitting the complex variables of the wave equations into the corresponding real parts and imaginary parts, sequentially substituting the split complex variables into the wave equations with deriving the coupled equations equivalent to the original wave equations, where the infinite free space is truncated by the perfectly matched layers. Then, the topology optimization problems of electromagnetic waves are transformed into the forms defined on real functional spaces instead of complex functional spaces; the adjoint analysis of the topology optimization problems is implemented on real functional spaces with removing the variational of the conjugate operator; the self-consistent adjoint sensitivity is derived, and the phase-dependence problem is avoided for the derived structural topology. Several numerical examples are implemented to demonstrate the robustness of the derived self-consistent adjoint analysis.

Electrostatics of DNA-Functionalized Nanoparticles

NASA Astrophysics Data System (ADS)

Hoffmann, Kyle; Krishnamoorthy, Kurinji; Kewalramani, Sumit; Bedzyk, Michael; Olvera de La Cruz, Monica

DNA-functionalized nanoparticles have applications in directed self-assembly and targeted cellular delivery of therapeutic proteins. In order to design specific systems, it is necessary to understand their self-assembly properties, of which the long-range electrostatic interactions are a critical component. We iteratively solved equations derived from classical density functional theory in order to predict the distribution of ions around DNA-functionalized Cg Catalase. We then compared estimates of the resonant intensity to those from SAXS measurements to estimate key features of DNA-functionalized proteins, such as the size of the region linking the protein and DNA and the extension of the single-stranded DNA. Using classical density functional theory and coarse-grained simulations, we are able to predict and understand these fundamental properties in order to rationally design new biomaterials.

Performance analysis of boron nitride embedded armchair graphene nanoribbon metal-oxide-semiconductor field effect transistor with Stone Wales defects

NASA Astrophysics Data System (ADS)

Chanana, Anuja; Sengupta, Amretashis; Mahapatra, Santanu

2014-01-01

We study the performance of a hybrid Graphene-Boron Nitride armchair nanoribbon (a-GNR-BN) n-MOSFET at its ballistic transport limit. We consider three geometric configurations 3p, 3p + 1, and 3p + 2 of a-GNR-BN with BN atoms embedded on either side (2, 4, and 6 BN) on the GNR. Material properties like band gap, effective mass, and density of states of these H-passivated structures are evaluated using the Density Functional Theory. Using these material parameters, self-consistent Poisson-Schrodinger simulations are carried out under the Non Equilibrium Green's Function formalism to calculate the ballistic n-MOSFET device characteristics. For a hybrid nanoribbon of width ˜5 nm, the simulated ON current is found to be in the range of 265 μA-280 μA with an ON/OFF ratio 7.1 × 106-7.4 × 106 for a VDD = 0.68 V corresponding to 10 nm technology node. We further study the impact of randomly distributed Stone Wales (SW) defects in these hybrid structures and only 2.5% degradation of ON current is observed for SW defect density of 3.18%.

A density functional theory study of self-regenerating catalysts LaFe(1-x)M(x)O(3-y) (M = Pd, Rh, Pt).

PubMed

Hamada, Ikutaro; Uozumi, Akifumi; Morikawa, Yoshitada; Yanase, Akira; Katayama-Yoshida, Hiroshi

2011-11-23

Periodic density functional theory was used to investigate the stability and electronic structures of precious-metal atoms in the vicinity of LaFe(1-x)M(x)O(3) (M = Pd, Rh, Pt) perovskite catalyst surfaces. It was found that the surface segregation of Pd and Pt is significantly stabilized by the introduction of O vacancies, whereas the solid-solution phase is favorable for Rh, suggesting an important role of O vacancies in the self-regeneration of Pd and Pt. On the basis of the results, we propose a possible scenario for the self-regeneration of the precious metal in the perovskite catalyst.

Interactions between Nanoparticles and Polymer Brushes: Molecular Dynamics Simulations and Self-consistent Field Theory Calculations

NASA Astrophysics Data System (ADS)

Cheng, Shengfeng; Wen, Chengyuan; Egorov, Sergei

2015-03-01

Molecular dynamics simulations and self-consistent field theory calculations are employed to study the interactions between a nanoparticle and a polymer brush at various densities of chains grafted to a plane. Simulations with both implicit and explicit solvent are performed. In either case the nanoparticle is loaded to the brush at a constant velocity. Then a series of simulations are performed to compute the force exerted on the nanoparticle that is fixed at various distances from the grafting plane. The potential of mean force is calculated and compared to the prediction based on a self-consistent field theory. Our simulations show that the explicit solvent leads to effects that are not captured in simulations with implicit solvent, indicating the importance of including explicit solvent in molecular simulations of such systems. Our results also demonstrate an interesting correlation between the force on the nanoparticle and the density profile of the brush. We gratefully acknowledge the support of NVIDIA Corporation with the donation of the Tesla K40 GPU used for this research.

Self-consistent phonon theory of the crystallization and elasticity of attractive hard spheres.

PubMed

Shin, Homin; Schweizer, Kenneth S

2013-02-28

We propose an Einstein-solid, self-consistent phonon theory for the crystal phase of hard spheres that interact via short-range attractions. The approach is first tested against the known behavior of hard spheres, and then applied to homogeneous particles that interact via short-range square well attractions and the Baxter adhesive hard sphere model. Given the crystal symmetry, packing fraction, and strength and range of attractive interactions, an effective harmonic potential experienced by a particle confined to its Wigner-Seitz cell and corresponding mean square vibrational amplitude are self-consistently calculated. The crystal free energy is then computed and, using separate information about the fluid phase free energy, phase diagrams constructed, including a first-order solid-solid phase transition and its associated critical point. The simple theory qualitatively captures all the many distinctive features of the phase diagram (critical and triple point, crystal-fluid re-entrancy, low-density coexistence curve) as a function of attraction range, and overall is in good semi-quantitative agreement with simulation. Knowledge of the particle localization length allows the crystal shear modulus to be estimated based on elementary ideas. Excellent predictions are obtained for the hard sphere crystal. Expanded and condensed face-centered cubic crystals are found to have qualitatively different elastic responses to varying attraction strength or temperature. As temperature increases, the expanded entropic solid stiffens, while the energy-controlled, fully-bonded dense solid softens.

Improved Electrostatic Embedding for Fragment-Based Chemical Shift Calculations in Molecular Crystals.

PubMed

Hartman, Joshua D; Balaji, Ashwin; Beran, Gregory J O

2017-12-12

Fragment-based methods predict nuclear magnetic resonance (NMR) chemical shielding tensors in molecular crystals with high accuracy and computational efficiency. Such methods typically employ electrostatic embedding to mimic the crystalline environment, and the quality of the results can be sensitive to the embedding treatment. To improve the quality of this embedding environment for fragment-based molecular crystal property calculations, we borrow ideas from the embedded ion method to incorporate self-consistently polarized Madelung field effects. The self-consistent reproduction of the Madelung potential (SCRMP) model developed here constructs an array of point charges that incorporates self-consistent lattice polarization and which reproduces the Madelung potential at all atomic sites involved in the quantum mechanical region of the system. The performance of fragment- and cluster-based 1 H, 13 C, 14 N, and 17 O chemical shift predictions using SCRMP and density functionals like PBE and PBE0 are assessed. The improved embedding model results in substantial improvements in the predicted 17 O chemical shifts and modest improvements in the 15 N ones. Finally, the performance of the model is demonstrated by examining the assignment of the two oxygen chemical shifts in the challenging γ-polymorph of glycine. Overall, the SCRMP-embedded NMR chemical shift predictions are on par with or more accurate than those obtained with the widely used gauge-including projector augmented wave (GIPAW) model.

Functional consistency across two behavioural modalities: fire-setting and self-harm in female special hospital patients.

PubMed

Miller, Sarah; Fritzon, Katarina

2007-01-01

Fire-setting and self-harm behaviours among women in high security special hospitals may be understood using Shye's Action System Theory (AST) in which four functional modes are recognized: 'adaptive', 'expressive', 'integrative', and 'conservative'. To test for relationships between different forms of fire-setting and self-harm behaviours and AST modes among women in special hospital, and for consistency within modes across the two behaviours. Clinical case files evidencing both fire-setting and self-harm behaviours (n = 50) were analysed for content, focusing on incident characteristics. A total of 29 fire-setting and 22 self-harm variables were analysed using Smallest Space Analysis (SSA). Chi-square and Spearman's rho (rho) analyses were used to determine functional consistency across behavioural modes. Most women showed one predominant AST mode in fire-setting (n = 39) and self-harm (n = 35). Significant positive correlations were found between integrative and adaptive modes of functioning. The lack of correlation between conservative and expressive modes reflects the differing behaviours used in each activity. Despite this, significant cross-tabulations revealed that each woman had parallel fire-setting and self-harm styles. Findings suggest that, for some women, setting fires and self harm fulfil a similar underlying function. Support is given to AST as a way of furthering understanding of damaging behaviours, whether self- or other-inflicted. Copyright 2007 John Wiley & Sons, Ltd.

Self-consistent gyrokinetic modeling of neoclassical and turbulent impurity transport

NASA Astrophysics Data System (ADS)

Estève, D.; Sarazin, Y.; Garbet, X.; Grandgirard, V.; Breton, S.; Donnel, P.; Asahi, Y.; Bourdelle, C.; Dif-Pradalier, G.; Ehrlacher, C.; Emeriau, C.; Ghendrih, Ph.; Gillot, C.; Latu, G.; Passeron, C.

2018-03-01

Trace impurity transport is studied with the flux-driven gyrokinetic GYSELA code (Grandgirard et al 2016 Comput. Phys. Commun. 207 35). A reduced and linearized multi-species collision operator has been recently implemented, so that both neoclassical and turbulent transport channels can be treated self-consistently on an equal footing. In the Pfirsch-Schlüter regime that is probably relevant for tungsten, the standard expression for the neoclassical impurity flux is shown to be recovered from gyrokinetics with the employed collision operator. Purely neoclassical simulations of deuterium plasma with trace impurities of helium, carbon and tungsten lead to impurity diffusion coefficients, inward pinch velocities due to density peaking, and thermo-diffusion terms which quantitatively agree with neoclassical predictions and NEO simulations (Belli et al 2012 Plasma Phys. Control. Fusion 54 015015). The thermal screening factor appears to be less than predicted analytically in the Pfirsch-Schlüter regime, which can be detrimental to fusion performance. Finally, self-consistent nonlinear simulations have revealed that the tungsten impurity flux is not the sum of turbulent and neoclassical fluxes computed separately, as is usually assumed. The synergy partly results from the turbulence-driven in-out poloidal asymmetry of tungsten density. This result suggests the need for self-consistent simulations of impurity transport, i.e. including both turbulence and neoclassical physics, in view of quantitative predictions for ITER.

Fabrication of high-density In3Sb1Te2 phase change nanoarray on glass-fabric reinforced flexible substrate

NASA Astrophysics Data System (ADS)

Yoon, Jong Moon; Shin, Dong Ok; Yin, You; Seo, Hyeon Kook; Kim, Daewoon; In Kim, Yong; Jin, Jung Ho; Kim, Yong Tae; Bae, Byeong-Soo; Ouk Kim, Sang; Lee, Jeong Yong

2012-06-01

Mushroom-shaped phase change memory (PCM) consisting of a Cr/In3Sb1Te2 (IST)/TiN (bottom electrode) nanoarray was fabricated via block copolymer lithography and single-step dry etching with a gas mixture of Ar/Cl2. The process was performed on a high performance transparent glass-fabric reinforced composite film (GFR Hybrimer) suitable for use as a novel substrate for flexible devices. The use of GFR Hybrimer with low thermal expansion and flat surfaces enabled successful nanoscale patterning of functional phase change materials on flexible substrates. Block copolymer lithography employing asymmetrical block copolymer blends with hexagonal cylindrical self-assembled morphologies resulted in the creation of hexagonal nanoscale PCM cell arrays with an areal density of approximately 176 Gb/in2.

Electronic energy level alignment at metal-molecule interfaces with a GW approach

NASA Astrophysics Data System (ADS)

Tamblyn, Isaac; Darancet, Pierre; Quek, Su Ying; Bonev, Stanimir A.; Neaton, Jeffrey B.

2011-11-01

Using density functional theory and many-body perturbation theory within a GW approximation, we calculate the electronic structure of a metal-molecule interface consisting of benzene diamine (BDA) adsorbed on Au(111). Through direct comparison with photoemission data, we show that a conventional G0W0 approach can underestimate the energy of the adsorbed molecular resonance relative to the Au Fermi level by up to 0.8 eV. The source of this discrepancy is twofold: a 0.7 eV underestimate of the gas phase ionization energy (IE), and a 0.2 eV overestimate of the Au work function. Refinements to self-energy calculations within the GW framework that account for deviations in both the Au work function and BDA gas-phase IE can result in an interfacial electronic level alignment in quantitative agreement with experiment.

Effect of ladder diagrams on optical absorption spectra in a quasiparticle self-consistent GW framework

NASA Astrophysics Data System (ADS)

Cunningham, Brian; Grüning, Myrta; Azarhoosh, Pooya; Pashov, Dimitar; van Schilfgaarde, Mark

2018-03-01

We present an approach to calculate the optical absorption spectra that combines the quasiparticle self-consistent GW method [Phys. Rev. B 76, 165106 (2007), 10.1103/PhysRevB.76.165106] for the electronic structure with the solution of the ladder approximation to the Bethe-Salpeter equation for the macroscopic dielectric function. The solution of the Bethe-Salpeter equation has been implemented within an all-electron framework, using a linear muffin-tin orbital basis set, with the contribution from the nonlocal self-energy to the transition dipole moments (in the optical limit) evaluated explicitly. This approach addresses those systems whose electronic structure is poorly described within the standard perturbative GW approaches with density-functional theory calculations as a starting point. The merits of this approach have been exemplified by calculating optical absorption spectra of a strongly correlated transition metal oxide, NiO, and a narrow gap semiconductor, Ge. In both cases, the calculated spectrum is in good agreement with the experiment. It is also shown that for systems whose electronic structure is well-described within the standard perturbative GW , such as Si, LiF, and h -BN , the performance of the present approach is in general comparable to the standard GW plus Bethe-Salpeter equation. It is argued that both vertex corrections to the electronic screening and the electron-phonon interaction are responsible for the observed systematic overestimation of the fundamental band gap and spectrum onset.

Understanding the effects of packing and chemical terminations on the optical excitations of azobenzene-functionalized self-assembled monolayers

NASA Astrophysics Data System (ADS)

Cocchi, Caterina; Draxl, Claudia

2017-10-01

In a first-principles study based on many-body perturbation theory, we analyze the optical excitations of azobenzene-functionalized self-assembled monolayers (SAMs) with increasing packing density and different terminations, considering for comparison the corresponding gas-phase molecules and dimers. Intermolecular coupling increases with the density of the chromophores independently of the functional groups. The intense π → π* resonance that triggers photo-isomerization is present in the spectra of isolated dimers and diluted SAMs, but it is almost completely washed out in tightly packed architectures. Intermolecular coupling is partially inhibited by mixing differently functionalized azobenzene derivatives, in particular when large groups are involved. In this way, the excitation band inducing the photo-isomerization process is partially preserved and the effects of dense packing partly counterbalanced. Our results suggest that a tailored design of azobenzene-functionalized SAMs which optimizes the interplay between the packing density of the chromophores and their termination can lead to significant improvements in the photo-switching efficiency of these systems.

Self-assembled monolayer structures of hexadecylamine on Cu surfaces: density-functional theory.

PubMed

Liu, Shih-Hsien; Balankura, Tonnam; Fichthorn, Kristen A

2016-12-07

We used dispersion-corrected density-functional theory to probe possible structures for adsorbed layers of hexadecylamine (HDA) on Cu(100) and Cu(111). HDA forms self-assembled layers on these surfaces, analogous to alkanethiols on various metal surfaces, and it binds by donating electrons in the amine group to the Cu surface atoms, consistent with experiment. van der Waals interactions between the alkyl tails of HDA molecules are stronger than the interaction between the amine group and the Cu surfaces. Strong HDA-tail interactions lead to coverage-dependent tilting of the HDA layers, such that the tilt angle is larger for lower coverages. At full monolayer coverage, the energetically preferred binding configuration for HDA on Cu(100) is a (5 × 3) pattern - although we cannot rule out incommensurate structures - while the pattern is preferred on Cu(111). A major motivation for this study is to understand the experimentally observed capability of HDA as a capping agent for producing {100}-faceted Cu nanocrystals. Consistent with experiment, we find that HDA binds more strongly to Cu(100) than to Cu(111). This strong binding stems from the capability of HDA to form more densely packed layers on Cu(100), which leads to stronger HDA-tail interactions, as well as the stronger binding of the amine group to Cu(100). We estimate the surface energies of HDA-covered Cu(100) and Cu(111) surfaces and find that these surfaces are nearly isoenergetic. By drawing analogies to previous theoretical work, it seems likely that HDA-covered Cu nanocrystals could have kinetic shapes that primarily express {100} facets, as is seen experimentally.

2-D Modeling of Nanoscale MOSFETs: Non-Equilibrium Green's Function Approach

NASA Technical Reports Server (NTRS)

Svizhenko, Alexei; Anantram, M. P.; Govindan, T. R.; Biegel, Bryan

2001-01-01

We have developed physical approximations and computer code capable of realistically simulating 2-D nanoscale transistors, using the non-equilibrium Green's function (NEGF) method. This is the most accurate full quantum model yet applied to 2-D device simulation. Open boundary conditions and oxide tunneling are treated on an equal footing. Electrons in the ellipsoids of the conduction band are treated within the anisotropic effective mass approximation. Electron-electron interaction is treated within Hartree approximation by solving NEGF and Poisson equations self-consistently. For the calculations presented here, parallelization is performed by distributing the solution of NEGF equations to various processors, energy wise. We present simulation of the "benchmark" MIT 25nm and 90nm MOSFETs and compare our results to those from the drift-diffusion simulator and the quantum-corrected results available. In the 25nm MOSFET, the channel length is less than ten times the electron wavelength, and the electron scattering time is comparable to its transit time. Our main results are: (1) Simulated drain subthreshold current characteristics are shown, where the potential profiles are calculated self-consistently by the corresponding simulation methods. The current predicted by our quantum simulation has smaller subthreshold slope of the Vg dependence which results in higher threshold voltage. (2) When gate oxide thickness is less than 2 nm, gate oxide leakage is a primary factor which determines off-current of a MOSFET (3) Using our 2-D NEGF simulator, we found several ways to drastically decrease oxide leakage current without compromising drive current. (4) Quantum mechanically calculated electron density is much smaller than the background doping density in the poly silicon gate region near oxide interface. This creates an additional effective gate voltage. Different ways to. include this effect approximately will be discussed.

Genarris: Random generation of molecular crystal structures and fast screening with a Harris approximation

NASA Astrophysics Data System (ADS)

Li, Xiayue; Curtis, Farren S.; Rose, Timothy; Schober, Christoph; Vazquez-Mayagoitia, Alvaro; Reuter, Karsten; Oberhofer, Harald; Marom, Noa

2018-06-01

We present Genarris, a Python package that performs configuration space screening for molecular crystals of rigid molecules by random sampling with physical constraints. For fast energy evaluations, Genarris employs a Harris approximation, whereby the total density of a molecular crystal is constructed via superposition of single molecule densities. Dispersion-inclusive density functional theory is then used for the Harris density without performing a self-consistency cycle. Genarris uses machine learning for clustering, based on a relative coordinate descriptor developed specifically for molecular crystals, which is shown to be robust in identifying packing motif similarity. In addition to random structure generation, Genarris offers three workflows based on different sequences of successive clustering and selection steps: the "Rigorous" workflow is an exhaustive exploration of the potential energy landscape, the "Energy" workflow produces a set of low energy structures, and the "Diverse" workflow produces a maximally diverse set of structures. The latter is recommended for generating initial populations for genetic algorithms. Here, the implementation of Genarris is reported and its application is demonstrated for three test cases.

Controlled release of functional proteins through designer self-assembling peptide nanofiber hydrogel scaffold

PubMed Central

Koutsopoulos, Sotirios; Unsworth, Larry D.; Nagai, Yusuke; Zhang, Shuguang

2009-01-01

The release kinetics for a variety of proteins of a wide range of molecular mass, hydrodynamic radii, and isoelectric points through a nanofiber hydrogel scaffold consisting of designer self-assembling peptides were studied by using single-molecule fluorescence correlation spectroscopy (FCS). In contrast to classical diffusion experiments, the single-molecule approach allowed for the direct determination of diffusion coefficients for lysozyme, trypsin inhibitor, BSA, and IgG both inside the hydrogel and after being released into the solution. The results of the FCS analyses and the calculated pristine in-gel diffusion coefficients were compared with the values obtained from the Stokes–Einstein equation, Fickian diffusion models, and the literature. The release kinetics suggested that protein diffusion through nanofiber hydrogels depended primarily on the size of the protein. Protein diffusivities decreased, with increasing hydrogel nanofiber density providing a means of controlling the release kinetics. Secondary and tertiary structure analyses and biological assays of the released proteins showed that encapsulation and release did not affect the protein conformation and functionality. Our results show that this biocompatible and injectable designer self-assembling peptide hydrogel system may be useful as a carrier for therapeutic proteins for sustained release applications. PMID:19273853

Spatial self-organization of macroscopic quantum states of exciton-polaritons in acoustic lattices

NASA Astrophysics Data System (ADS)

Buller, J. V. T.; Cerda-Méndez, E. A.; Balderas-Navarro, R. E.; Biermann, K.; Santos, P. V.

2016-07-01

Exciton-polariton systems can sustain macroscopic quantum states (MQSs) under a periodic potential modulation. In this paper, we investigate the structure of these states in acoustic square lattices by probing their wave functions in real and momentum spaces using spectral tomography. We show that the polariton MQSs, when excited by a Gaussian laser beam, self-organize in a concentric structure, consisting of a single, two-dimensional gap-soliton (GS) state surrounded by one dimensional (1D) MQSs with lower energy. The latter form at hyperbolical points of the modulated polariton dispersion. While the size of the GS tends to saturate with increasing particle density, the emission region of the surrounding 1D states increases. The existence of these MQSs in acoustic lattices is quantitatively supported by a theoretical model based on the variational solution of the Gross-Pitaevskii equation. The formation of the 1D states in a ring around the central GS is attributed to the energy gradient in this region, which reduces the overall symmetry of the lattice. The results broaden the experimental understanding of self-localized polariton states, which may prove relevant for functionalities exploiting solitonic objects.

Excitation spectra of aromatic molecules within a real-space G W -BSE formalism: Role of self-consistency and vertex corrections

DOE PAGES

Hung, Linda; da Jornada, Felipe H.; Souto-Casares, Jaime; ...

2016-08-15

Here, we present first-principles calculations on the vertical ionization potentials (IPs), electron affinities (EAs), and singlet excitation energies on an aromatic-molecule test set (benzene, thiophene, 1,2,5-thiadiazole, naphthalene, benzothiazole, and tetrathiafulvalene) within the GW and Bethe-Salpeter equation (BSE) formalisms. Our computational framework, which employs a real-space basis for ground-state and a transition-space basis for excited-state calculations, is well suited for high-accuracy calculations on molecules, as we show by comparing against G0W0 calculations within a plane-wave-basis formalism. We then generalize our framework to test variants of the GW approximation that include a local density approximation (LDA)–derived vertex function (Γ LDA ) andmore » quasiparticle-self-consistent (QS) iterations. We find that Γ LDA and quasiparticle self-consistency shift IPs and EAs by roughly the same magnitude, but with opposite sign for IPs and the same sign for EAs. G0W0 and QS GWΓ LDA are more accurate for IPs, while G 0W 0Γ LDA and QS GW are best for EAs. For optical excitations, we find that perturbative GW-BSE underestimates the singlet excitation energy, while self-consistent GW-BSE results in good agreement with previous best-estimate values for both valence and Rydberg excitations. Finally, our work suggests that a hybrid approach, in which G0W0 energies are used for occupied orbitals and G0W0Γ LDA for unoccupied orbitals, also yields optical excitation energies in good agreement with experiment but at a smaller computational cost.« less

Excitation spectra of aromatic molecules within a real-space G W -BSE formalism: Role of self-consistency and vertex corrections

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hung, Linda; da Jornada, Felipe H.; Souto-Casares, Jaime

Here, we present first-principles calculations on the vertical ionization potentials (IPs), electron affinities (EAs), and singlet excitation energies on an aromatic-molecule test set (benzene, thiophene, 1,2,5-thiadiazole, naphthalene, benzothiazole, and tetrathiafulvalene) within the GW and Bethe-Salpeter equation (BSE) formalisms. Our computational framework, which employs a real-space basis for ground-state and a transition-space basis for excited-state calculations, is well suited for high-accuracy calculations on molecules, as we show by comparing against G0W0 calculations within a plane-wave-basis formalism. We then generalize our framework to test variants of the GW approximation that include a local density approximation (LDA)–derived vertex function (Γ LDA ) andmore » quasiparticle-self-consistent (QS) iterations. We find that Γ LDA and quasiparticle self-consistency shift IPs and EAs by roughly the same magnitude, but with opposite sign for IPs and the same sign for EAs. G0W0 and QS GWΓ LDA are more accurate for IPs, while G 0W 0Γ LDA and QS GW are best for EAs. For optical excitations, we find that perturbative GW-BSE underestimates the singlet excitation energy, while self-consistent GW-BSE results in good agreement with previous best-estimate values for both valence and Rydberg excitations. Finally, our work suggests that a hybrid approach, in which G0W0 energies are used for occupied orbitals and G0W0Γ LDA for unoccupied orbitals, also yields optical excitation energies in good agreement with experiment but at a smaller computational cost.« less

Current rectification by self-assembled molecular quantum dots from first principles

NASA Astrophysics Data System (ADS)

Larade, Brian; Bratkovsky, Alexander

2003-03-01

We present results of first-principles calculations of the current rectification by self-assembled molecular quantum dots. Molecules of that kind should be synthesized with a central conjugated (narrow band-gap) part, and two peripheral saturated (wide band-gap) barrier groups of substantially different lengths L1 and L_2. The peripheral groups must end with chemical Â"anchorÂ" groups, enabling attachment of the molecule to the electrodes. In such molecules, if they are not longer than about 2-3 nm, the electron transport is likely to proceed by resonant tunneling through molecular orbitals (MO) centered on the conjugated part of the molecule (Â"quantum dotÂ") [1,2]. Generally, either LUMO (lowest unoccupied MO) or HOMO (highest occupied MO) will be most transparent to the tunneling electrons because of their different coupling to electrodes. We have studied (i) single benzene ring C6H6 [2] and (ii) naphthalene C10H8, separated from gold electrodes by alkane chains of different lengths with the use of the non-equilibrium Green's function method and self-consistent density-functional theory. The results show significant changes in electron density and potential distribution in the vicinity of molecule-electrode contact. In the case of a naphthalene quantum dot, separated from electrodes by asymmetric alkane groups (CH2)2 and (CH2)6, the I-V curve shows current rectification on the order of ˜ 10^2. [1] A.M. Bratkovsky and P.E. Kornilovitch, Phys. Rev. B (2002), to be published. [2] P. E. Kornilovitch, A.M. Bratkovsky, and R.S. Williams, Phys. Rev. B 66, 165436 (2002).

Charging in the ac Conductance of a Double Barrier Resonant Tunneling Structure

NASA Technical Reports Server (NTRS)

Anantram, M. P.; Saini, Subhash (Technical Monitor)

1998-01-01

There have been many studies of the linear response ac conductance of a double barrier resonant tunneling structure (DBRTS), both at zero and finite dc biases. While these studies are important, they fail to self consistently include the effect of the time dependent charge density in the well. In this paper, we calculate the ac conductance at both zero and finite do biases by including the effect of the time dependent charge density in the well in a self consistent manner. The charge density in the well contributes to both the flow of displacement currents in the contacts and the time dependent potential in the well. We find that including these effects can make a significant difference to the ac conductance and the total ac current is not equal to the simple average of the non-selfconsistently calculated conduction currents in the two contacts. This is illustrated by comparing the results obtained with and without the effect of the time dependent charge density included correctly. Some possible experimental scenarios to observe these effects are suggested.

Self-consistent calculation of the nuclear composition in hot and dense stellar matter

NASA Astrophysics Data System (ADS)

Furusawa, Shun; Mishustin, Igor

2017-03-01

We investigate the mass fractions and in-medium properties of heavy nuclei in stellar matter at characteristic densities and temperatures for supernova (SN) explosions. The individual nuclei are described within the compressible liquid-drop model taking into account modifications of bulk, surface, and Coulomb energies. The equilibrium properties of nuclei and the full ensemble of heavy nuclei are calculated self-consistently. It is found that heavy nuclei in the ensemble are either compressed or decompressed depending on the isospin asymmetry of the system. The compression or decompression has a little influence on the binding energies, total mass fractions, and average mass numbers of heavy nuclei, although the equilibrium densities of individual nuclei themselves are changed appreciably above one-hundredth of normal nuclear density. We find that nuclear structure in the single-nucleus approximation deviates from the actual one obtained in the multinucleus description, since the density of free nucleons is different between these two descriptions. This study indicates that a multinucleus description is required to realistically account for in-medium effects on the nuclear structure in supernova matter.

Time-dependent density-functional theory with optimized effective potential and self-interaction correction and derivative discontinuity for the treatment of double ionization of He and Be atoms in intense laser fields

NASA Astrophysics Data System (ADS)

Heslar, John; Telnov, Dmitry A.; Chu, Shih-I.

2013-05-01

We present a self-interaction-free time-dependent density-functional theory (TDDFT) for the treatment of double-ionization processes of many-electron systems. The method is based on the extension of the Krieger-Li-Iafrate (KLI) treatment of the optimized effective potential (OEP) theory and the incorporation of an explicit self-interaction correction (SIC) term. In the framework of the time-dependent density functional theory, we have performed three-dimensional (3D) calculations of double ionization of He and Be atoms by intense near-infrared laser fields. We make use of the exchange-correlation potential with the integer discontinuity which improves the description of the double-ionization process. We found that a proper description of the double ionization requires the TDDFT exchange-correlation potential with the discontinuity with respect to the variation of the total particle number (TPN). The results for the intensity-dependent rates of double ionization of He and Be atoms are presented.

Density Functional Calculations of Native Defects in CH 3 NH 3 PbI 3 : Effects of Spin–Orbit Coupling and Self-Interaction Error

DOE PAGES

Du, Mao-Hua

2015-04-02

We know that native point defects play an important role in carrier transport properties of CH3NH3PbI3. However, the nature of many important defects remains controversial due partly to the conflicting results reported by recent density functional theory (DFT) calculations. In this Letter, we show that self-interaction error and the neglect of spin–orbit coupling (SOC) in many previous DFT calculations resulted in incorrect positions of valence and conduction band edges, although their difference, which is the band gap, is in good agreement with the experimental value. Moreover, this problem has led to incorrect predictions of defect-level positions. Hybrid density functional calculations,more » which partially correct the self-interaction error and include the SOC, show that, among native point defects (including vacancies, interstitials, and antisites), only the iodine vacancy and its complexes induce deep electron and hole trapping levels inside of the band gap, acting as nonradiative recombination centers.« less

Invited Paper - Density functional theory: coverage of dynamic and non-dynamic electron correlation effects

NASA Astrophysics Data System (ADS)

Cremer, Dieter

The electron correlation effects covered by density functional theory (DFT) can be assessed qualitatively by comparing DFT densities ρ(r) with suitable reference densities obtained with wavefunction theory (WFT) methods that cover typical electron correlation effects. The analysis of difference densities ρ(DFT)-ρ(WFT) reveals that LDA and GGA exchange (X) functionals mimic non-dynamic correlation effects in an unspecified way. It is shown that these long range correlation effects are caused by the self-interaction error (SIE) of standard X functionals. Self-interaction corrected (SIC) DFT exchange gives, similar to exact exchange, for the bonding region a delocalized exchange hole, and does not cover any correlation effects. Hence, the exchange SIE is responsible for the fact that DFT densities often resemble MP4 or MP2 densities. The correlation functional changes X-only DFT densities in a manner observed when higher order coupling effects between lower order N-electron correlation effects are included. Hybrid functionals lead to changes in the density similar to those caused by SICDFT, which simply reflects the fact that hybrid functionals have been developed to cover part of the SIE and its long range correlation effects in a balanced manner. In the case of spin-unrestricted DFT (UDFT), non-dynamic electron correlation effects enter the calculation both via the X functional and via the wavefunction, which may cause a double-counting of correlation effects. The use of UDFT in the form of permuted orbital and broken-symmetry DFT (PO-UDFT, BS-UDFT) can lead to reasonable descriptions of multireference systems provided certain conditions are fulfilled. More reliable, however, is a combination of DFT and WFT methods, which makes the routine description of multireference systems possible. The development of such methods implies a separation of dynamic and non-dynamic correlation effects. Strategies for accomplishing this goal are discussed in general and tested in practice for CAS (complete active space)-DFT.

Self-consistent models for Coulomb-heated X-ray pulsar atmospheres

NASA Technical Reports Server (NTRS)

Harding, A. K.; Kirk, J. G.; Galloway, D. J.; Meszaros, P.

1984-01-01

Calculations of accreting magnetized neutron star atmospheres heated by the gradual deceleration of Protons via Coulomb collisions are presented. Self consistent determinations of the temperature and density structure for different accretion rates are made by assuming hydrostatic equilibrium and energy balance, coupled with radiative transfer. The full radiative transfer in two polarizations, using magnetic cross sections but with cyclotron resonance effects treated approximately, is carried out in the inhomogeneous atmospheres. Previously announced in STAR as N84-12012

Disorder and superfluid density in overdoped cuprate superconductors

NASA Astrophysics Data System (ADS)

Lee-Hone, N. R.; Dodge, J. S.; Broun, D. M.

2017-07-01

We calculate superfluid density for a dirty d -wave superconductor. The effects of impurity scattering are treated within the self-consistent t -matrix approximation, in weak-coupling BCS theory. Working from a realistic tight-binding parametrization of the Fermi surface, we find a superfluid density that is both correlated with Tc and linear in temperature, in good correspondence with recent experiments on overdoped La2 -xSrxCuO4 .

Approximate solution of the mode-mode coupling integral: Application to cytosine and its deuterated derivative.

PubMed

Rasheed, Tabish; Ahmad, Shabbir

2010-10-01

Ab initio Hartree-Fock (HF), density functional theory (DFT) and second-order Møller-Plesset (MP2) methods were used to perform harmonic and anharmonic calculations for the biomolecule cytosine and its deuterated derivative. The anharmonic vibrational spectra were computed using the vibrational self-consistent field (VSCF) and correlation-corrected vibrational self-consistent field (CC-VSCF) methods. Calculated anharmonic frequencies have been compared with the argon matrix spectra reported in literature. The results were analyzed with focus on the properties of anharmonic couplings between pair of modes. A simple and easy to use formula for calculation of mode-mode coupling magnitudes has been derived. The key element in present approach is the approximation that only interactions between pairs of normal modes have been taken into account, while interactions of triples or more are neglected. FTIR and Raman spectra of solid state cytosine have been recorded in the regions 400-4000 cm(-1) and 60-4000 cm(-1), respectively. Vibrational analysis and assignments are based on calculated potential energy distribution (PED) values. Copyright 2010 Elsevier B.V. All rights reserved.

Self-consistent phonon calculations of lattice dynamical properties in cubic SrTiO3 with first-principles anharmonic force constants

NASA Astrophysics Data System (ADS)

Tadano, Terumasa; Tsuneyuki, Shinji

2015-08-01

We present an ab initio framework to calculate anharmonic phonon frequency and phonon lifetime that is applicable to severely anharmonic systems. We employ self-consistent phonon (SCPH) theory with microscopic anharmonic force constants, which are extracted from density functional calculations using the least absolute shrinkage and selection operator technique. We apply the method to the high-temperature phase of SrTiO3 and obtain well-defined phonon quasiparticles that are free from imaginary frequencies. Here we show that the anharmonic phonon frequency of the antiferrodistortive mode depends significantly on the system size near the critical temperature of the cubic-to-tetragonal phase transition. By applying perturbation theory to the SCPH result, phonon lifetimes are calculated for cubic SrTiO3, which are then employed to predict lattice thermal conductivity using the Boltzmann transport equation within the relaxation-time approximation. The presented methodology is efficient and accurate, paving the way toward a reliable description of thermodynamic, dynamic, and transport properties of systems with severe anharmonicity, including thermoelectric, ferroelectric, and superconducting materials.

The QTP family of consistent functionals and potentials in Kohn-Sham density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Yifan; Bartlett, Rodney J., E-mail: bartlett@qtp.ufl.edu

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 propertiesmore » such as geometries, reaction barrier heights, and atomization energies.« less

The local density of optical states of a metasurface

NASA Astrophysics Data System (ADS)

Lunnemann, Per; Koenderink, A. Femius

2016-02-01

While metamaterials are often desirable for near-field functions, such as perfect lensing, or cloaking, they are often quantified by their response to plane waves from the far field. Here, we present a theoretical analysis of the local density of states near lattices of discrete magnetic scatterers, i.e., the response to near field excitation by a point source. Based on a pointdipole theory using Ewald summation and an array scanning method, we can swiftly and semi-analytically evaluate the local density of states (LDOS) for magnetoelectric point sources in front of an infinite two-dimensional (2D) lattice composed of arbitrary magnetoelectric dipole scatterers. The method takes into account radiation damping as well as all retarded electrodynamic interactions in a self-consistent manner. We show that a lattice of magnetic scatterers evidences characteristic Drexhage oscillations. However, the oscillations are phase shifted relative to the electrically scattering lattice consistent with the difference expected for reflection off homogeneous magnetic respectively electric mirrors. Furthermore, we identify in which source-surface separation regimes the metasurface may be treated as a homogeneous interface, and in which homogenization fails. A strong frequency and in-plane position dependence of the LDOS close to the lattice reveals coupling to guided modes supported by the lattice.

A review on ab initio studies of static, transport, and optical properties of polystyrene under extreme conditions for inertial confinement fusion applications

NASA Astrophysics Data System (ADS)

Hu, S. X.; Collins, L. A.; Boehly, T. R.; Ding, Y. H.; Radha, P. B.; Goncharov, V. N.; Karasiev, V. V.; Collins, G. W.; Regan, S. P.; Campbell, E. M.

2018-05-01

Polystyrene (CH), commonly known as "plastic," has been one of the widely used ablator materials for capsule designs in inertial confinement fusion (ICF). Knowing its precise properties under high-energy-density conditions is crucial to understanding and designing ICF implosions through radiation-hydrodynamic simulations. For this purpose, systematic ab initio studies on the static, transport, and optical properties of CH, in a wide range of density and temperature conditions (ρ = 0.1 to 100 g/cm3 and T = 103 to 4 × 106 K), have been conducted using quantum molecular dynamics (QMD) simulations based on the density functional theory. We have built several wide-ranging, self-consistent material-properties tables for CH, such as the first-principles equation of state, the QMD-based thermal conductivity (κQMD) and ionization, and the first-principles opacity table. This paper is devoted to providing a review on (1) what results were obtained from these systematic ab initio studies; (2) how these self-consistent results were compared with both traditional plasma-physics models and available experiments; and (3) how these first-principles-based properties of polystyrene affect the predictions of ICF target performance, through both 1-D and 2-D radiation-hydrodynamic simulations. In the warm dense regime, our ab initio results, which can significantly differ from predictions of traditional plasma-physics models, compared favorably with experiments. When incorporated into hydrocodes for ICF simulations, these first-principles material properties of CH have produced significant differences over traditional models in predicting 1-D/2-D target performance of ICF implosions on OMEGA and direct-drive-ignition designs for the National Ignition Facility. Finally, we will discuss the implications of these studies on the current small-margin ICF target designs using a CH ablator.

Dissipative quantum hydrodynamics model of x-ray Thomson scattering in dense plasmas

NASA Astrophysics Data System (ADS)

Diaw, Abdourahmane; Murillo, Michael

2017-10-01

X-ray Thomson scattering (XRTS) provides detailed diagnostic information about dense plasma experiments. The inferences made rely on an accurate model for the form factor, which is typically expressed in terms of a well-known response function. Here, we develop an alternate approach based on quantum hydrodynamics using a viscous form of dynamical density functional theory. This approach is shown to include the equation of state self-consistently, including sum rules, as well as irreversibility arising from collisions. This framework is used to generate a model for the scattering spectrum, and it offers an avenue for measuring hydrodynamic properties, such as transport coefficients, using XRTS. This work was supported by the Air Force Office of Scientific Research (Grant No. FA9550-12-1-0344).

Ab initio quantum chemistry: methodology and applications.

PubMed

Friesner, Richard A

2005-05-10

This Perspective provides an overview of state-of-the-art ab initio quantum chemical methodology and applications. The methods that are discussed include coupled cluster theory, localized second-order Moller-Plesset perturbation theory, multireference perturbation approaches, and density functional theory. The accuracy of each approach for key chemical properties is summarized, and the computational performance is analyzed, emphasizing significant advances in algorithms and implementation over the past decade. Incorporation of a condensed-phase environment by means of mixed quantum mechanical/molecular mechanics or self-consistent reaction field techniques, is presented. A wide range of illustrative applications, focusing on materials science and biology, are discussed briefly.

The Self-Organization of a Spoken Word

PubMed Central

Holden, John G.; Rajaraman, Srinivasan

2012-01-01

Pronunciation time probability density and hazard functions from large speeded word naming data sets were assessed for empirical patterns consistent with multiplicative and reciprocal feedback dynamics – interaction dominant dynamics. Lognormal and inverse power law distributions are associated with multiplicative and interdependent dynamics in many natural systems. Mixtures of lognormal and inverse power law distributions offered better descriptions of the participant’s distributions than the ex-Gaussian or ex-Wald – alternatives corresponding to additive, superposed, component processes. The evidence for interaction dominant dynamics suggests fundamental links between the observed coordinative synergies that support speech production and the shapes of pronunciation time distributions. PMID:22783213

High-throughput ab-initio dilute solute diffusion database.

PubMed

Wu, Henry; Mayeshiba, Tam; Morgan, Dane

2016-07-19

We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world.

First-Principles Study of the Self-Assembled Pentacene Molecules on Metal Surfaces

NASA Astrophysics Data System (ADS)

Lee, Kyuho; Han, Myung-Joon; Yu, Jaejun

2003-03-01

Oriented thin films of organic semiconducting small molecules have received considerable attention as active semiconductors for device applications such as Schottky diodes and thin-film transistors (TFTs). Among these organic materials, pentacene has been found to have the highest mobilities for hole transport. Understanding the formation of self-organized ad-layers of pentacene would contribute to the fabrication of nanostructures and possibly highly oriented pentacene layers by epitaxy for use in electronic devices. To understand the ordering patterns of pentacene ad-layers on metal surfaces, we investigated the energetics between pentacene molecules with and without metal substrates and analyzed its electronic structure. We used a self-consistent first-principles calculation method based on the density functional theory (DFT) within local density approximation (LDA). The localized pseudo-atomic orbitals (PAO) are employed for a real-space numerical basis set, which was suggested by Sankey and Niklewski, and the Troullier-Martins-type pseudo-potential is used. As results, we found that the ordering patterns can be explained by the energetics between pentacene molecules, and the metal substrates appears not to influence too much on the interaction between pentacenes. To investigate the nature of the self-assembled structure, we calculated the total energies of various configurations for the molecule pattern, e.g., side-by-side and head-to-head ordering or on-top stacking. Depending on its direction, extremely different interaction character between two pentacenes is found and explained by its electronic structure analysis.

Multiconfiguration pair-density functional theory for doublet excitation energies and excited state geometries: the excited states of CN.

PubMed

Bao, Jie J; Gagliardi, Laura; Truhlar, Donald G

2017-11-15

Multiconfiguration pair-density functional theory (MC-PDFT) is a post multiconfiguration self-consistent field (MCSCF) method with similar performance to complete active space second-order perturbation theory (CASPT2) but with greater computational efficiency. Cyano radical (CN) is a molecule whose spectrum is well established from experiments and whose excitation energies have been used as a testing ground for theoretical methods to treat excited states of open-shell systems, which are harder and much less studied than excitation energies of closed-shell singlets. In the present work, we studied the adiabatic excitation energies of CN with MC-PDFT. Then we compared this multireference (MR) method to some single-reference (SR) methods, including time-dependent density functional theory (TDDFT) and completely renormalized equation-of-motion coupled-cluster theory with singles, doubles and noniterative triples [CR-EOM-CCSD(T)]; we also compared to some other MR methods, including configuration interaction singles and doubles (MR-CISD) and multistate CASPT2 (MS-CASPT2). Through a comparison between SR and MR methods, we achieved a better appreciation of the need to use MR methods to accurately describe higher excited states, and we found that among the MR methods, MC-PDFT stands out for its accuracy for the first four states out of the five doublet states studied this paper; this shows its efficiency for calculating doublet excited states.

Einasto profiles and the dark matter power spectrum

NASA Astrophysics Data System (ADS)

Ludlow, Aaron D.; Angulo, Raúl E.

2017-02-01

We study the mass accretion histories (MAHs) and density profiles of dark matter haloes using N-body simulations of self-similar gravitational clustering from scale-free power spectra, P(k) ∝ kn. We pay particular attention to the density profile curvature, which we characterize using the shape parameter, α, of an Einasto profile. In agreement with previous findings, our results suggest that, despite vast differences in their MAHs, the density profiles of virialized haloes are remarkably alike. Nonetheless, clear departures from self-similarity are evident: For a given spectral index, α increases slightly but systematically with `peak height', ν ≡ δsc/σ(M, z), regardless of mass or redshift. More importantly, however, the `α-ν' relation depends on n: The steeper the initial power spectrum, the more gradual the curvature of both the mean MAHs and mean density profiles. These results are consistent with previous findings connecting the shapes of halo mass profiles and MAHs, and imply that dark matter haloes are not structurally self-similar but, through the merger history, retain a memory of the linear density field from which they form.

Reply to "Comment on 'A Self-Consistent Model of the Interacting Ring Current Ions and Electromagnetic Ion Cyclotron Waves, Initial Results: Waves and Precipitation Fluxes' and 'Self-Consistent Model of the Magnetospheric Ring Current and Propagating Electromagnetic Ion Cyclotron Waves: Waves in Multi-Ion Magnetosphere' by Khazanov et al. et al."

NASA Technical Reports Server (NTRS)

Khazanov, G. V.; Gamayunov, K. V.; Gallagher, D. L.; Kozyra, J. W.

2007-01-01

It is well-known that the effects of electromagnetic ion cyclotron (EMIC) waves on ring current (RC) ion and radiation belt (RB) electron dynamics strongly depend on such particle/wave characteristics as the phase-space distribution function, frequency, wavenormal angle, wave energy, and the form of wave spectral energy density. The consequence is that accurate modeling of EMIC waves and RC particles requires robust inclusion of the interdependent dynamics of wave growth/damping, wave propagation, and[ particles. Such a self-consistent model is being progressively developed by Khazanov et al. [2002, 2006, 2007]. This model is based on a system of coupled kinetic equations for the RC and EMIC wave power spectral density along with the ray tracing equations. Thome and Home [2007] (hereafter referred to as TH2007) call the Khazanov et al. [2002, 2006] results into question in their Comment. The points in contention can be summarized as follows. TH2007 claim that: (1) "the important damping of waves by thermal heavy ions is completely ignored", and Landau damping during resonant interaction with thermal electrons is not included in our model; (2) EMIC wave damping due to RC O + is not included in our simulation; (3) non-linear processes limiting EMIC wave amplitude are not included in our model; (4) growth of the background fluctuations to a physically significantamplitude"must occur during a single transit of the unstable region" with subsequent damping below bi-ion latitudes,and consequently"the bounce averaged wave kinetic equation employed in the code contains a physically erroneous 'assumption". Our reply will address each of these points as well as other criticisms mentioned in the Comment. TH2007 are focused on two of our papers that are separated by four years. Significant progress in the self-consistent treatment of the RC-EMIC wave system has been achieved during those years. The paper by Khazanov et al. [2006] presents the latest version of our model, and in this Reply we refer mostly to this paper.

Quantum many-body intermetallics: Phase stability of Fe3Al and small-gap formation in Fe2VAl

NASA Astrophysics Data System (ADS)

Kristanovski, Oleg; Richter, Raphael; Krivenko, Igor; Lichtenstein, Alexander I.; Lechermann, Frank

2017-01-01

Various intermetallic compounds harbor subtle electronic correlation effects. To elucidate this fact for the Fe-Al system, we perform a realistic many-body investigation based on a combination of density functional theory with dynamical mean-field theory in a charge self-consistent manner. A better characterization and understanding of the phase stability of bcc-based D 03-Fe3Al through an improved description of the correlated charge density and the magnetic energy is achieved. Upon replacement of one Fe sublattice with V, the Heusler compound Fe2VAl is realized, known to display bad-metal behavior and increased specific heat. Here we document a charge-gap opening at low temperatures in line with previous experimental work. The gap structure does not match conventional band theory and is reminiscent of (pseudo)gap characteristics in correlated oxides.

Equilibrium stellar systems with spindle singularities

NASA Technical Reports Server (NTRS)

Shapiro, Stuart L.; Teukolsky, Saul A.

1992-01-01

Equilibrium sequences of axisymmetric Newtonian clusters that tend toward singular states are constructed. The distribution functions are chosen to be of the form f = f(E, Jz). The numerical method then determines the density and gravitational potential self-consistently to satisfy Poisson's equation. For the prolate models, spindle singularities arise from the depletion of angular momentum near the symmetry axis. While the resulting density enhancement is confined to the region near the axis, the influence of the spindle extends much further out through its tidal gravitational field. Centrally condensed prolate clusters may contain strong-field regions even though the spindle mass is small and the mean cluster eccentricity is not extreme. While the calculations performed here are entirely Newtonian, the issue of singularities is an important topic in general relativity. Equilibrium solutions for relativistic star clusters can provide a testing ground for exploring this issue. The methods used in this paper for building nonspherical clusters can be extended to relativistic systems.

Theoretical investigation of the electron capture and loss processes in the collisions of He2+ + Ne.

PubMed

Hong, Xuhai; Wang, Feng; Jiao, Yalong; Su, Wenyong; Wang, Jianguo; Gou, Bingcong

2013-08-28

Based on the time-dependent density functional theory, a method is developed to study ion-atom collision dynamics, which self-consistently couples the quantum mechanical description of electron dynamics with the classical treatment of the ion motion. Employing real-time and real-space method, the coordinate space translation technique is introduced to allow one to focus on the region of target or projectile depending on the actual concerned process. The benchmark calculations are performed for the collisions of He(2+) + Ne, and the time evolution of electron density distribution is monitored, which provides interesting details of the interaction dynamics between the electrons and ion cores. The cross sections of single and many electron capture and loss have been calculated in the energy range of 1-1000 keV/amu, and the results show a good agreement with the available experiments over a wide range of impact energies.

Formation of orbital-selective electron states in LaTiO3/SrTiO3 superlattices

NASA Astrophysics Data System (ADS)

Lechermann, Frank; Boehnke, Lewin; Grieger, Daniel

2013-06-01

The interface electronic structure of correlated LaTiO3/SrTiO3 superlattices is investigated by means of the charge self-consistent combination of the local density approximation (LDA) to density functional theory with dynamical mean-field theory. Utilizing a pseudopotential technique together with a continuous-time quantum Monte Carlo approach, the resulting complex multiorbital electronic states are addressed in a coherent fashion beyond static mean field. General structural relaxations are taken into account on the LDA level and cooperate with the driving forces from strong electronic correlations. This alliance leads to a Ti(3dxy) dominated low-energy quasiparticle peak and a lower Hubbard band in line with photoemission studies. Furthermore correlation effects close to the band-insulating bulk SrTiO3 limit as well as the Mott-insulating bulk LaTiO3 limit are studied via realistic single-layer embeddings.

Excitation of propagating magnetization waves by microstrip antennas

NASA Astrophysics Data System (ADS)

Dmitriev, V. F.; Kalinikos, B. A.

1988-11-01

We discuss the self-consistent theory of excitation of dipole-exchange magnetization waves by microstrip antennas in a metal-dielectric-ferrite-dielectric-metal stratified structure, magnetized under an arbitrary angle to the surface. Spin-wave Green's functions are derived, describing the response of the spin-system to a spatially inhomogeneous varying magnetic field. The radiative resistance of microstrip antenna is calculated. In this case the distribution of surface current density in the antenna is found on the basis of the analytic solution of a singular integral equation. The nature of the effect of metallic screens and redistributed surface current densities in the antenna on the frequency dependence of the resistive radiation is investigated. Approximate relations are obtained, convenient for practical calculations of radiative resistance of microstrip antennas both in a free and in a screened ferromagnetic film. The theoretical calculations are verified by data of experiments carried out on monocrystalline films of iron-yttrium garnet.

Calculated high-pressure structural properties, lattice dynamics and quasi particle band structures of perovskite fluorides KZnF3, CsCaF3 and BaLiF3

NASA Astrophysics Data System (ADS)

Vaitheeswaran, G.; Kanchana, V.; Zhang, Xinxin; Ma, Yanming; Svane, A.; Christensen, N. E.

2016-08-01

A detailed study of the high-pressure structural properties, lattice dynamics and band structures of perovskite structured fluorides KZnF3, CsCaF3 and BaLiF3 has been carried out by means of density functional theory. The calculated structural properties including elastic constants and equation of state agree well with available experimental information. The phonon dispersion curves are in good agreement with available experimental inelastic neutron scattering data. The electronic structures of these fluorides have been calculated using the quasi particle self-consistent GW approximation. The GW calculations reveal that all the fluorides studied are wide band gap insulators, and the band gaps are significantly larger than those obtained by the standard local density approximation, thus emphasizing the importance of quasi particle corrections in perovskite fluorides.

Simultaneous determination of effective carrier lifetime and resistivity of Si wafers using the nonlinear nature of photocarrier radiometric signals

NASA Astrophysics Data System (ADS)

Sun, Qiming; Melnikov, Alexander; Wang, Jing; Mandelis, Andreas

2018-04-01

A rigorous treatment of the nonlinear behavior of photocarrier radiometric (PCR) signals is presented theoretically and experimentally for the quantitative characterization of semiconductor photocarrier recombination and transport properties. A frequency-domain model based on the carrier rate equation and the classical carrier radiative recombination theory was developed. The derived concise expression reveals different functionalities of the PCR amplitude and phase channels: the phase bears direct quantitative correlation with the carrier effective lifetime, while the amplitude versus the estimated photocarrier density dependence can be used to extract the equilibrium majority carrier density and thus, resistivity. An experimental ‘ripple’ optical excitation mode (small modulation depth compared to the dc level) was introduced to bypass the complicated ‘modulated lifetime’ problem so as to simplify theoretical interpretation and guarantee measurement self-consistency and reliability. Two Si wafers with known resistivity values were tested to validate the method.

Ab-initio atomic level stress and role of d-orbitals in CuZr, CuZn and CuY

NASA Astrophysics Data System (ADS)

Ojha, Madhusudan; Nicholson, Don M.; Egami, Takeshi

2015-03-01

Atomic level stress offers a new tool to characterize materials within the local approximation to density functional theory (DFT). Ab-initio atomic level stresses in B2 structures of CuZr, CuZn and CuY are calculated and results are explained on the basis of d-orbital contributions to Density of States (DOS). The overlap of d-orbital DOS plays an important role in the relative magnitude of atomic level stresses in these structures. The trends in atomic level stresses that we observed in these simple B2 structures are also seen in complex structures such as liquids, glasses and solid solutions. The stresses are however modified by the different coordination and relaxed separation distances in these complex structures. We used the Locally Self-Consistent Multiple Scattering (LSMS) code and Vienna Ab-initio Simulation Package (VASP) for ab-initio calculations.

Calculated high-pressure structural properties, lattice dynamics and quasi particle band structures of perovskite fluorides KZnF3, CsCaF3 and BaLiF3.

PubMed

Vaitheeswaran, G; Kanchana, V; Zhang, Xinxin; Ma, Yanming; Svane, A; Christensen, N E

2016-08-10

A detailed study of the high-pressure structural properties, lattice dynamics and band structures of perovskite structured fluorides KZnF3, CsCaF3 and BaLiF3 has been carried out by means of density functional theory. The calculated structural properties including elastic constants and equation of state agree well with available experimental information. The phonon dispersion curves are in good agreement with available experimental inelastic neutron scattering data. The electronic structures of these fluorides have been calculated using the quasi particle self-consistent [Formula: see text] approximation. The [Formula: see text] calculations reveal that all the fluorides studied are wide band gap insulators, and the band gaps are significantly larger than those obtained by the standard local density approximation, thus emphasizing the importance of quasi particle corrections in perovskite fluorides.

Adaptation of the projector-augmented-wave formalism to the treatment of orbital-dependent exchange-correlation functionals

NASA Astrophysics Data System (ADS)

Xu, Xiao; Holzwarth, N. A. W.

2011-10-01

This paper presents the formulation and numerical implementation of a self-consistent treatment of orbital-dependent exchange-correlation functionals within the projector-augmented-wave method of Blöchl [Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.50.17953 50, 17953 (1994)] for electronic structure calculations. The methodology is illustrated with binding energy curves for C in the diamond structure and LiF in the rock salt structure, by comparing results from the Hartree-Fock (HF) formalism and the optimized effective potential formalism in the so-called KLI approximation [Krieger, Li, and Iafrate, Phys. Rev. APLRAAN1050-294710.1103/PhysRevA.45.101 45, 101 (1992)] with those of the local density approximation. While the work here uses pure Fock exchange only, the formalism can be extended to treat orbital-dependent functionals more generally.

Communication: The description of strong correlation within self-consistent Green's function second-order perturbation theory

NASA Astrophysics Data System (ADS)

Phillips, Jordan J.; Zgid, Dominika

2014-06-01

We report an implementation of self-consistent Green's function many-body theory within a second-order approximation (GF2) for application with molecular systems. This is done by iterative solution of the Dyson equation expressed in matrix form in an atomic orbital basis, where the Green's function and self-energy are built on the imaginary frequency and imaginary time domain, respectively, and fast Fourier transform is used to efficiently transform these quantities as needed. We apply this method to several archetypical examples of strong correlation, such as a H32 finite lattice that displays a highly multireference electronic ground state even at equilibrium lattice spacing. In all cases, GF2 gives a physically meaningful description of the metal to insulator transition in these systems, without resorting to spin-symmetry breaking. Our results show that self-consistent Green's function many-body theory offers a viable route to describing strong correlations while remaining within a computationally tractable single-particle formalism.

Electronic charge rearrangement at metal/organic interfaces induced by weak van der Waals interactions

NASA Astrophysics Data System (ADS)

Ferri, Nicola; Ambrosetti, Alberto; Tkatchenko, Alexandre

2017-07-01

Electronic charge rearrangements at interfaces between organic molecules and solid surfaces play a key role in a wide range of applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. It is common to utilize electrostatics and Pauli pushback to control the interface electronic properties, while the ubiquitous van der Waals (vdW) interactions are often considered to have a negligible direct contribution (beyond the obvious structural relaxation). Here, we apply a fully self-consistent Tkatchenko-Scheffler vdW density functional to demonstrate that the weak vdW interactions can induce sizable charge rearrangements at hybrid metal/organic systems (HMOS). The complex vdW correlation potential smears out the interfacial electronic density, thereby reducing the charge transfer in HMOS, changes the interface work functions by up to 0.2 eV, and increases the interface dipole moment by up to 0.3 Debye. Our results suggest that vdW interactions should be considered as an additional control parameter in the design of hybrid interfaces with the desired electronic properties.

Effect of the nonlocal exchange on the performance of the orbital-dependent correlation functionals from second-order perturbation theory.

PubMed

Schweigert, Igor V; Bartlett, Rodney J

2008-09-28

Adding a fraction of the nonlocal exchange operator to the local orbital-dependent exchange potential improves the many-body perturbation expansion based on the Kohn-Sham determinant. The effect of such a hybrid scheme on the performance of the orbital-dependent correlation functional from the second-order perturbation theory (PT2H) is investigated numerically. A small fraction of the nonlocal exchange is often sufficient to ensure the existence of the self-consistent solution for the PT2H potential. In the He and Be atoms, including 37% of the nonlocal exchange leads to the correlation energies and electronic densities that are very close to the exact ones. In molecules, varying the fraction of the nonlocal exchange may result in the PT2H energy closely reproducing the CCSD(T) value; however such a fraction depends on the system and does not always result in an accurate electronic density. We also numerically verify that the "semicanonical" perturbation series includes most of the beneficial effects of the nonlocal exchange without sacrificing the locality of the exchange potential.

Counterintuitive electron localisation from density-functional theory with polarisable solvent models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dale, Stephen G., E-mail: sdale@ucmerced.edu; Johnson, Erin R., E-mail: erin.johnson@dal.ca

2015-11-14

Exploration of the solvated electron phenomena using density-functional theory (DFT) generally results in prediction of a localised electron within an induced solvent cavity. However, it is well known that DFT favours highly delocalised charges, rendering the localisation of a solvated electron unexpected. We explore the origins of this counterintuitive behaviour using a model Kevan-structure system. When a polarisable-continuum solvent model is included, it forces electron localisation by introducing a strong energetic bias that favours integer charges. This results in the formation of a large energetic barrier for charge-hopping and can cause the self-consistent field to become trapped in local minimamore » thus converging to stable solutions that are higher in energy than the ground electronic state. Finally, since the bias towards integer charges is caused by the polarisable continuum, these findings will also apply to other classical polarisation corrections, as in combined quantum mechanics and molecular mechanics (QM/MM) methods. The implications for systems beyond the solvated electron, including cationic DNA bases, are discussed.« less

Simple vertex correction improves G W band energies of bulk and two-dimensional crystals

NASA Astrophysics Data System (ADS)

Schmidt, Per S.; Patrick, Christopher E.; Thygesen, Kristian S.

2017-11-01

The G W self-energy method has long been recognized as the gold standard for quasiparticle (QP) calculations of solids in spite of the fact that the neglect of vertex corrections and the use of a density-functional theory starting point lack rigorous justification. In this work we remedy this situation by including a simple vertex correction that is consistent with a local-density approximation starting point. We analyze the effect of the self-energy by splitting it into short-range and long-range terms which are shown to govern, respectively, the center and size of the band gap. The vertex mainly improves the short-range correlations and therefore has a small effect on the band gap, while it shifts the band gap center up in energy by around 0.5 eV, in good agreement with experiments. Our analysis also explains how the relative importance of short- and long-range interactions in structures of different dimensionality is reflected in their QP energies. Inclusion of the vertex comes at practically no extra computational cost and even improves the basis set convergence compared to G W . Taken together, the method provides an efficient and rigorous improvement over the G W approximation.

Canonical-ensemble state-averaged complete active space self-consistent field (SA-CASSCF) strategy for problems with more diabatic than adiabatic states: Charge-bond resonance in monomethine cyanines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olsen, Seth, E-mail: seth.olsen@uq.edu.au

2015-01-28

This paper reviews basic results from a theory of the a priori classical probabilities (weights) in state-averaged complete active space self-consistent field (SA-CASSCF) models. It addresses how the classical probabilities limit the invariance of the self-consistency condition to transformations of the complete active space configuration interaction (CAS-CI) problem. Such transformations are of interest for choosing representations of the SA-CASSCF solution that are diabatic with respect to some interaction. I achieve the known result that a SA-CASSCF can be self-consistently transformed only within degenerate subspaces of the CAS-CI ensemble density matrix. For uniformly distributed (“microcanonical”) SA-CASSCF ensembles, self-consistency is invariant tomore » any unitary CAS-CI transformation that acts locally on the ensemble support. Most SA-CASSCF applications in current literature are microcanonical. A problem with microcanonical SA-CASSCF models for problems with “more diabatic than adiabatic” states is described. The problem is that not all diabatic energies and couplings are self-consistently resolvable. A canonical-ensemble SA-CASSCF strategy is proposed to solve the problem. For canonical-ensemble SA-CASSCF, the equilibrated ensemble is a Boltzmann density matrix parametrized by its own CAS-CI Hamiltonian and a Lagrange multiplier acting as an inverse “temperature,” unrelated to the physical temperature. Like the convergence criterion for microcanonical-ensemble SA-CASSCF, the equilibration condition for canonical-ensemble SA-CASSCF is invariant to transformations that act locally on the ensemble CAS-CI density matrix. The advantage of a canonical-ensemble description is that more adiabatic states can be included in the support of the ensemble without running into convergence problems. The constraint on the dimensionality of the problem is relieved by the introduction of an energy constraint. The method is illustrated with a complete active space valence-bond (CASVB) analysis of the charge/bond resonance electronic structure of a monomethine cyanine: Michler’s hydrol blue. The diabatic CASVB representation is shown to vary weakly for “temperatures” corresponding to visible photon energies. Canonical-ensemble SA-CASSCF enables the resolution of energies and couplings for all covalent and ionic CASVB structures contributing to the SA-CASSCF ensemble. The CASVB solution describes resonance of charge- and bond-localized electronic structures interacting via bridge resonance superexchange. The resonance couplings can be separated into channels associated with either covalent charge delocalization or chemical bonding interactions, with the latter significantly stronger than the former.« less

Canonical-ensemble state-averaged complete active space self-consistent field (SA-CASSCF) strategy for problems with more diabatic than adiabatic states: charge-bond resonance in monomethine cyanines.

PubMed

Olsen, Seth

2015-01-28

This paper reviews basic results from a theory of the a priori classical probabilities (weights) in state-averaged complete active space self-consistent field (SA-CASSCF) models. It addresses how the classical probabilities limit the invariance of the self-consistency condition to transformations of the complete active space configuration interaction (CAS-CI) problem. Such transformations are of interest for choosing representations of the SA-CASSCF solution that are diabatic with respect to some interaction. I achieve the known result that a SA-CASSCF can be self-consistently transformed only within degenerate subspaces of the CAS-CI ensemble density matrix. For uniformly distributed ("microcanonical") SA-CASSCF ensembles, self-consistency is invariant to any unitary CAS-CI transformation that acts locally on the ensemble support. Most SA-CASSCF applications in current literature are microcanonical. A problem with microcanonical SA-CASSCF models for problems with "more diabatic than adiabatic" states is described. The problem is that not all diabatic energies and couplings are self-consistently resolvable. A canonical-ensemble SA-CASSCF strategy is proposed to solve the problem. For canonical-ensemble SA-CASSCF, the equilibrated ensemble is a Boltzmann density matrix parametrized by its own CAS-CI Hamiltonian and a Lagrange multiplier acting as an inverse "temperature," unrelated to the physical temperature. Like the convergence criterion for microcanonical-ensemble SA-CASSCF, the equilibration condition for canonical-ensemble SA-CASSCF is invariant to transformations that act locally on the ensemble CAS-CI density matrix. The advantage of a canonical-ensemble description is that more adiabatic states can be included in the support of the ensemble without running into convergence problems. The constraint on the dimensionality of the problem is relieved by the introduction of an energy constraint. The method is illustrated with a complete active space valence-bond (CASVB) analysis of the charge/bond resonance electronic structure of a monomethine cyanine: Michler's hydrol blue. The diabatic CASVB representation is shown to vary weakly for "temperatures" corresponding to visible photon energies. Canonical-ensemble SA-CASSCF enables the resolution of energies and couplings for all covalent and ionic CASVB structures contributing to the SA-CASSCF ensemble. The CASVB solution describes resonance of charge- and bond-localized electronic structures interacting via bridge resonance superexchange. The resonance couplings can be separated into channels associated with either covalent charge delocalization or chemical bonding interactions, with the latter significantly stronger than the former.

Comparing ab initio density-functional and wave function theories: the impact of correlation on the electronic density and the role of the correlation potential.

PubMed

Grabowski, Ireneusz; Teale, Andrew M; Śmiga, Szymon; Bartlett, Rodney J

2011-09-21

The framework of ab initio density-functional theory (DFT) has been introduced as a way to provide a seamless connection between the Kohn-Sham (KS) formulation of DFT and wave-function based ab initio approaches [R. J. Bartlett, I. Grabowski, S. Hirata, and S. Ivanov, J. Chem. Phys. 122, 034104 (2005)]. Recently, an analysis of the impact of dynamical correlation effects on the density of the neon atom was presented [K. Jankowski, K. Nowakowski, I. Grabowski, and J. Wasilewski, J. Chem. Phys. 130, 164102 (2009)], contrasting the behaviour for a variety of standard density functionals with that of ab initio approaches based on second-order Møller-Plesset (MP2) and coupled cluster theories at the singles-doubles (CCSD) and singles-doubles perturbative triples [CCSD(T)] levels. In the present work, we consider ab initio density functionals based on second-order many-body perturbation theory and coupled cluster perturbation theory in a similar manner, for a range of small atomic and molecular systems. For comparison, we also consider results obtained from MP2, CCSD, and CCSD(T) calculations. In addition to this density based analysis, we determine the KS correlation potentials corresponding to these densities and compare them with those obtained for a range of ab initio density functionals via the optimized effective potential method. The correlation energies, densities, and potentials calculated using ab initio DFT display a similar systematic behaviour to those derived from electronic densities calculated using ab initio wave function theories. In contrast, typical explicit density functionals for the correlation energy, such as VWN5 and LYP, do not show behaviour consistent with this picture of dynamical correlation, although they may provide some degree of correction for already erroneous explicitly density-dependent exchange-only functionals. The results presented here using orbital dependent ab initio density functionals show that they provide a treatment of exchange and correlation contributions within the KS framework that is more consistent with traditional ab initio wave function based methods.

Self-assembly of a binodal metal-organic framework exhibiting a demi-regular lattice.

PubMed

Yan, Linghao; Kuang, Guowen; Zhang, Qiushi; Shang, Xuesong; Liu, Pei Nian; Lin, Nian

2017-10-26

Designing metal-organic frameworks with new topologies is a long-standing quest because new topologies often accompany new properties and functions. Here we report that 1,3,5-tris[4-(pyridin-4-yl)phenyl]benzene molecules coordinate with Cu atoms to form a two-dimensional framework in which Cu adatoms form a nanometer-scale demi-regular lattice. The lattice is articulated by perfectly arranged twofold and threefold pyridyl-Cu coordination motifs in a ratio of 1 : 6 and features local dodecagonal symmetry. This structure is thermodynamically robust and emerges solely when the molecular density is at a critical value. In comparison, we present three framework structures that consist of semi-regular and regular lattices of Cu atoms self-assembled out of 1,3,5-tris[4-(pyridin-4-yl)phenyl]benzene and trispyridylbenzene molecules. Thus a family of regular, semi-regular and demi-regular lattices can be achieved by Cu-pyridyl coordination.

Extremely asymmetric phase diagram of homopolymer-monotethered nanoparticles: Competition between chain conformational entropy and particle steric interaction.

PubMed

Zhang, Tiancai; Fu, Chao; Yang, Yingzi; Qiu, Feng

2017-02-07

The phase behaviors of homopolymer-monotethered nanoparticles (HMNs) in melt are investigated via a theoretical method combining self-consistent field theory for polymers and density functional theory for hard spheres. An extremely asymmetric phase diagram is observed: (i) microphases are only possible for the volume fraction of the tethered polymer f A > 0.35; (ii) in addition to lamellar phase, the system can only self-assemble into various morphologies with a polymer-rich matrix, including gyroid phase, cylindrical phase, and spherical phase. In the frame of this theory, the critical point for HMNs' microphase separation is significantly lower than that of linear diblock copolymers. Furthermore, the characteristic length of microphase-separated structures of HMNs is much smaller than that of linear diblock copolymers with the same molecular weight. Our calculation results on morphologies and characteristic length agree well with recent simulations and experimental observations.

Hybrid-DFT  +  V w method for band structure calculation of semiconducting transition metal compounds: the case of cerium dioxide.

PubMed

Ivády, Viktor; Gali, Adam; Abrikosov, Igor A

2017-11-15

Hybrid functionals' non-local exchange-correlation potential contains a derivative discontinuity that improves on standard semi-local density functional theory (DFT) band gaps. Moreover, by careful parameterization, hybrid functionals can provide self-interaction reduced description of selected states. On the other hand, the uniform description of all the electronic states of a given system is a known drawback of these functionals that causes varying accuracy in the description of states with different degrees of localization. This limitation can be remedied by the orbital dependent exact exchange extension of hybrid functionals; the hybrid-DFT  +  V w method (Ivády et al 2014 Phys. Rev. B 90 035146). Based on the analogy of quasi-particle equations and hybrid-DFT single particle equations, here we demonstrate that parameters of hybrid-DFT  +  V w functional can be determined from approximate theoretical quasi-particle spectra without any fitting to experiment. The proposed method is illustrated on the charge self-consistent electronic structure calculation for cerium dioxide where itinerant valence states interact with well-localized 4f atomic like states, making this system challenging for conventional methods, either hybrid-DFT or LDA  +  U, and therefore allowing for a demonstration of the advantages of the proposed scheme.

Full-band quantum simulation of electron devices with the pseudopotential method: Theory, implementation, and applications

NASA Astrophysics Data System (ADS)

Pala, M. G.; Esseni, D.

2018-03-01

This paper presents the theory, implementation, and application of a quantum transport modeling approach based on the nonequilibrium Green's function formalism and a full-band empirical pseudopotential Hamiltonian. We here propose to employ a hybrid real-space/plane-wave basis that results in a significant reduction of the computational complexity compared to a full plane-wave basis. To this purpose, we provide a theoretical formulation in the hybrid basis of the quantum confinement, the self-energies of the leads, and the coupling between the device and the leads. After discussing the theory and the implementation of the new simulation methodology, we report results for complete, self-consistent simulations of different electron devices, including a silicon Esaki diode, a thin-body silicon field effect transistor (FET), and a germanium tunnel FET. The simulated transistors have technologically relevant geometrical features with a semiconductor film thickness of about 4 nm and a channel length ranging from 10 to 17 nm. We believe that the newly proposed formalism may find applications also in transport models based on ab initio Hamiltonians, as those employed in density functional theory methods.

Functional level-set derivative for a polymer self consistent field theory Hamiltonian

NASA Astrophysics Data System (ADS)

Ouaknin, Gaddiel; Laachi, Nabil; Bochkov, Daniil; Delaney, Kris; Fredrickson, Glenn H.; Gibou, Frederic

2017-09-01

We derive functional level-set derivatives for the Hamiltonian arising in self-consistent field theory, which are required to solve free boundary problems in the self-assembly of polymeric systems such as block copolymer melts. In particular, we consider Dirichlet, Neumann and Robin boundary conditions. We provide numerical examples that illustrate how these shape derivatives can be used to find equilibrium and metastable structures of block copolymer melts with a free surface in both two and three spatial dimensions.

The anabolic steroid nandrolone alters cannabinoid self-administration and brain CB1 receptor density and function.

PubMed

Struik, Dicky; Fadda, Paola; Zara, Tamara; Zamberletti, Erica; Rubino, Tiziana; Parolaro, Daniela; Fratta, Walter; Fattore, Liana

2017-01-01

Clinical and pre-clinical observations indicate that anabolic-androgenic steroids can induce neurobiological changes that alter the rewarding effects of drugs of abuse. In this study, we investigated the effect of the anabolic steroid nandrolone on the rewarding properties of the cannabinoid CB 1 receptor agonist WIN55,212-2 (WIN) in rats. Lister Hooded male rats were treated intramuscularly with nandrolone (15mg/kg) or vehicle for 14 consecutive days, and then allowed to self-administer WIN (12.5μg/kg/infusion) intravenously. After reaching stable drug intake, self-administration behavior was extinguished to examine drug- and cue-induced reinstatement of cannabinoid-seeking behavior. Other behavioral parameters presumed to influence drug-taking and drug-seeking behaviors were examined to gain more insight into the behavioral specificity of nandrolone treatment. Finally, animals were sacrificed for analysis of CB 1 receptor density and function in selected brain areas. We found that nandrolone-treated rats self-administered up to 2 times more cannabinoid than vehicle-treated rats, but behaved similarly to control rats when tested for drug- and cue-induced reinstatement of cannabinoid-seeking behavior. Enhanced cannabinoid intake by nandrolone-treated rats was not accompanied by changes in locomotor activity, sensorimotor gating, or memory function. However, our molecular data show that after chronic WIN self-administration nandrolone-treated rats display altered CB 1 receptor density and function in selected brain areas. We hypothesize that increased cannabinoid self-administration in nandrolone-treated rats results from a nandrolone-induced decrease in reward function, which rats seem to compensate by voluntarily increasing their cannabinoid intake. Altogether, our findings corroborate the hypothesis that chronic exposure to anabolic-androgenic steroids induces dysfunction of the reward pathway in rats and might represent a potential risk factor for abuse of cannabis and other drugs in humans. Copyright © 2016 Elsevier Ltd. All rights reserved.

Double counting in the density functional plus dynamical mean-field theory of transition metal oxides

NASA Astrophysics Data System (ADS)

Dang, Hung

2015-03-01

Recently, the combination of density functional theory (DFT) and dynamical mean-field theory (DMFT) has become a widely-used beyond-mean-field approach for strongly correlated materials. However, not only is the correlation treated in DMFT but also in DFT to some extent, a problem arises as the correlation is counted twice in the DFT+DMFT framework. The correction for this problem is still not well-understood. To gain more understanding of this ``double counting'' problem, I provide a detailed study of the metal-insulator transition in transition metal oxides in the subspace of oxygen p and transition metal correlated d orbitals using DFT+DMFT. I will show that the fully charge self-consistent DFT+DMFT calculations with the standard ``fully-localized limit'' (FLL) double counting correction fail to predict correctly materials such as LaTiO3, LaVO3, YTiO3 and SrMnO3 as insulators. Investigations in a wide range of the p- d splitting, the d occupancy, the lattice structure and the double counting correction itself will be presented to understand the reason behind this failure. I will also show that if the double counting correction is chosen to reproduce the p- d splitting consistent with experimental data, the DFT+DMFT approach can still give reasonable results in comparison with experiments.

Relativistic equation of state at subnuclear densities in the Thomas-Fermi approximation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Z. W.; Shen, H., E-mail: shennankai@gmail.com

We study the non-uniform nuclear matter using the self-consistent Thomas-Fermi approximation with a relativistic mean-field model. The non-uniform matter is assumed to be composed of a lattice of heavy nuclei surrounded by dripped nucleons. At each temperature T, proton fraction Y{sub p} , and baryon mass density ρ {sub B}, we determine the thermodynamically favored state by minimizing the free energy with respect to the radius of the Wigner-Seitz cell, while the nucleon distribution in the cell can be determined self-consistently in the Thomas-Fermi approximation. A detailed comparison is made between the present results and previous calculations in the Thomas-Fermimore » approximation with a parameterized nucleon distribution that has been adopted in the widely used Shen equation of state.« less

Self-shielding of hydrogen in the IGM during the epoch of reionization

NASA Astrophysics Data System (ADS)

Chardin, Jonathan; Kulkarni, Girish; Haehnelt, Martin G.

2018-04-01

We investigate self-shielding of intergalactic hydrogen against ionizing radiation in radiative transfer simulations of cosmic reionization carefully calibrated with Lyα forest data. While self-shielded regions manifest as Lyman-limit systems in the post-reionization Universe, here we focus on their evolution during reionization (redshifts z = 6-10). At these redshifts, the spatial distribution of hydrogen-ionizing radiation is highly inhomogeneous, and some regions of the Universe are still neutral. After masking the neutral regions and ionizing sources in the simulation, we find that the hydrogen photoionization rate depends on the local hydrogen density in a manner very similar to that in the post-reionization Universe. The characteristic physical hydrogen density above which self-shielding becomes important at these redshifts is about nH ˜ 3 × 10-3 cm-3, or ˜20 times the mean hydrogen density, reflecting the fact that during reionization photoionization rates are typically low enough that the filaments in the cosmic web are often self-shielded. The value of the typical self-shielding density decreases by a factor of 3 between redshifts z = 3 and 10, and follows the evolution of the average photoionization rate in ionized regions in a simple fashion. We provide a simple parameterization of the photoionization rate as a function of density in self-shielded regions during the epoch of reionization.

Self-shielding of hydrogen in the IGM during the epoch of reionization

NASA Astrophysics Data System (ADS)

Chardin, Jonathan; Kulkarni, Girish; Haehnelt, Martin G.

2018-07-01

We investigate self-shielding of intergalactic hydrogen against ionizing radiation in radiative transfer simulations of cosmic reionization carefully calibrated with Lyα forest data. While self-shielded regions manifest as Lyman limit systems in the post-reionization Universe, here we focus on their evolution during reionization (redshifts z = 6-10). At these redshifts, the spatial distribution of hydrogen-ionizing radiation is highly inhomogeneous, and some regions of the Universe are still neutral. After masking the neutral regions and ionizing sources in the simulation, we find that the hydrogen photoionization rate depends on the local hydrogen density in a manner very similar to that in the post-reionization Universe. The characteristic physical hydrogen density above which self-shielding becomes important at these redshifts is about nH ˜ 3 × 10-3 cm-3, or ˜20 times the mean hydrogen density, reflecting the fact that during reionization photoionization rates are typically low enough that the filaments in the cosmic web are often self-shielded. The value of the typical self-shielding density decreases by a factor of 3 between redshifts z = 3 and 10, and follows the evolution of the average photoionization rate in ionized regions in a simple fashion. We provide a simple parametrization of the photoionization rate as a function of density in self-shielded regions during the epoch of reionization.

An important rule for realizing metal → half-metal → semiconductor transition in single-molecule junctions

NASA Astrophysics Data System (ADS)

Zeng, Jing; Chen, Ke-Qiu; Long, Mengqiu

2017-06-01

Recently, Zhong et al (2015 Nano Lett. 15 8091) found that two additional hydrogen atoms can be adsorbed to the opposite aza-bridging nitrogen atoms of the manganese phthalocyanine (MnPc) macrocycle when exposed to H2. Thus the symmetry of the MnPc molecule is changed from 4-fold to 2-fold. Motivated by this recent experiment, we theoretically investigate a MnPc-based single-molecule junction in this work and propose a simple and reliable way to realize the transition of its electronic properties. On the basis of spin-polarized density-functional theory calculations combined with the Keldysh nonequilibrium Green’s technique, we find that the gradual hydrogenation in MnPc molecules gives rise to the changes of the hardness of the electron density and spin-selective orbital decoupling, which eventually leads to the realization of the first ever metal  →  half-metal  →  semiconductor transition behavior in single-molecule junctions. Analysis of molecular projected self-consistent Hamiltonian, Mulliken population, and local density of states also reveals an important rule for realizing this transition behavior. Our research confirms that the hydrogenation of MnPc molecules can realize various molecular functionalities in unitary material background.

Performance analysis of boron nitride embedded armchair graphene nanoribbon metal–oxide–semiconductor field effect transistor with Stone Wales defects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chanana, Anuja; Sengupta, Amretashis; Mahapatra, Santanu

2014-01-21

We study the performance of a hybrid Graphene-Boron Nitride armchair nanoribbon (a-GNR-BN) n-MOSFET at its ballistic transport limit. We consider three geometric configurations 3p, 3p + 1, and 3p + 2 of a-GNR-BN with BN atoms embedded on either side (2, 4, and 6 BN) on the GNR. Material properties like band gap, effective mass, and density of states of these H-passivated structures are evaluated using the Density Functional Theory. Using these material parameters, self-consistent Poisson-Schrodinger simulations are carried out under the Non Equilibrium Green's Function formalism to calculate the ballistic n-MOSFET device characteristics. For a hybrid nanoribbon of widthmore » ∼5 nm, the simulated ON current is found to be in the range of 265 μA–280 μA with an ON/OFF ratio 7.1 × 10{sup 6}–7.4 × 10{sup 6} for a V{sub DD} = 0.68 V corresponding to 10 nm technology node. We further study the impact of randomly distributed Stone Wales (SW) defects in these hybrid structures and only 2.5% degradation of ON current is observed for SW defect density of 3.18%.« less

Mass Transport in the Warm, Dense Matter and High-Energy Density Regimes

NASA Astrophysics Data System (ADS)

Kress, J. D.; Burakovsky, L.; Ticknor, C.; Collins, L. A.; Lambert, F.

2011-10-01

Large-scale hydrodynamical simulations of fluids and plasmas under extreme conditions require knowledge of certain microscopic properties such as diffusion and viscosity in addition to the equation-of-state. To determine these dynamical properties, we employ quantum molecular dynamical (MD) simulations on large samples of atoms. The method has several advantages: 1) static, dynamical, and optical properties are produced consistently from the same simulations, and 2) mixture properties arise in a natural way since all intra- and inter-particle interactions are properly represented. We utilize two forms of density functional theory: 1) Kohn-Sham (KS-DFT) and 2) orbital-free (OF-DFT). KS-DFT is computationally intense due to its reliance on an orbital representation. As the temperature rises, the Thomas-Fermi approximation in OF-DFT begins to represent accurately the density functional, and provides an efficient and systematic means for extending the quantum simulations to very hot conditions. We have performed KS-DFT and OF-DFT calculations of the self-diffusion, mutual diffusion and shear viscosity for Al, Li, H, and LiH. We examine trends in these quantities and compare to more approximate forms such as the one-component plasma model. We also determine the validity of mixing rules that combine the properties of pure species into a composite result.

Density distribution function of a self-gravitating isothermal compressible turbulent fluid in the context of molecular clouds ensembles

NASA Astrophysics Data System (ADS)

Donkov, Sava; Stefanov, Ivan Z.

2018-03-01

We have set ourselves the task of obtaining the probability distribution function of the mass density of a self-gravitating isothermal compressible turbulent fluid from its physics. We have done this in the context of a new notion: the molecular clouds ensemble. We have applied a new approach that takes into account the fractal nature of the fluid. Using the medium equations, under the assumption of steady state, we show that the total energy per unit mass is an invariant with respect to the fractal scales. As a next step we obtain a non-linear integral equation for the dimensionless scale Q which is the third root of the integral of the probability distribution function. It is solved approximately up to the leading-order term in the series expansion. We obtain two solutions. They are power-law distributions with different slopes: the first one is -1.5 at low densities, corresponding to an equilibrium between all energies at a given scale, and the second one is -2 at high densities, corresponding to a free fall at small scales.

Expansion of Titan atmosphere

NASA Astrophysics Data System (ADS)

Salem, S.; Moslem, W. M.; Radi, A.

2017-05-01

Self-similar plasma expansion approach is used to solve a plasma model based on the losing phenomenon of Titan atmospheric composition. To this purpose, a set of hydrodynamic fluid equations describing a plasma consisting of two positive ions with different masses and isothermal electrons is used. With the aid of self-similar transformation, numerical solution of the fluid equations has been performed to examine the density, velocity, and potential profiles. The effects of different plasma parameters, i.e., density and temperature ratios, are studied on the expanding plasma profiles. The present investigation could be useful to recognize the ionized particles escaping from Titan atmosphere.

Nonempirical Calculation of Superconducting Transition Temperatures in Light-Element Superconductors.

PubMed

Arita, Ryotaro; Koretsune, Takashi; Sakai, Shiro; Akashi, Ryosuke; Nomura, Yusuke; Sano, Wataru

2017-07-01

Recent progress in the fully nonempirical calculation of the superconducting transition temperature (T c ) is reviewed. Especially, this study focuses on three representative light-element high-T c superconductors, i.e., elemental Li, sulfur hydrides, and alkali-doped fullerides. Here, it is discussed how crucial it is to develop the beyond Migdal-Eliashberg (ME) methods. For Li, a scheme of superconducting density functional theory for the plasmon mechanism is formulated and it is found that T c is dramatically enhanced by considering the frequency dependence of the screened Coulomb interaction. For sulfur hydrides, it is essential to go beyond not only the static approximation for the screened Coulomb interaction, but also the constant density-of-states approximation for electrons, the harmonic approximation for phonons, and the Migdal approximation for the electron-phonon vertex, all of which have been employed in the standard ME calculation. It is also shown that the feedback effect in the self-consistent calculation of the self-energy and the zero point motion considerably affect the calculation of T c . For alkali-doped fullerides, the interplay between electron-phonon coupling and electron correlations becomes more nontrivial. It has been demonstrated that the combination of density functional theory and dynamical mean field theory with the ab initio downfolding scheme for electron-phonon coupled systems works successfully. This study not only reproduces the experimental phase diagram but also obtains a unified view of the high-T c superconductivity and the Mott-Hubbard transition in the fullerides. The results for these high-T c superconductors will provide a firm ground for future materials design of new superconductors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Hydrodynamic Theory for Spatially Inhomogeneous Semiconductor Lasers: Microscopic Approach

NASA Technical Reports Server (NTRS)

Li, Jianzhong; Ning, C. Z.; Biegel, Bryan A. (Technical Monitor)

2001-01-01

Starting from the microscopic semiconductor Bloch equations (SBEs) including the Boltzmann transport terms in the distribution function equations for electrons and holes, we derived a closed set of diffusion equations for carrier densities and temperatures with self-consistent coupling to Maxwell's equation and to an effective optical polarization equation. The coherent many-body effects are included within the screened Hartree-Fock approximation, while scatterings are treated within the second Born approximation including both the in- and out-scatterings. Microscopic expressions for electron-hole (e-h) and carrier-LO (c-LO) phonon scatterings are directly used to derive the momentum and energy relaxation rates. These rates expressed as functions of temperatures and densities lead to microscopic expressions for self- and mutual-diffusion coefficients in the coupled density-temperature diffusion equations. Approximations for reducing the general two-component description of the electron-hole plasma (EHP) to a single-component one are discussed. In particular, we show that a special single-component reduction is possible when e-h scattering dominates over c-LO phonon scattering. The ambipolar diffusion approximation is also discussed and we show that the ambipolar diffusion coefficients are independent of e-h scattering, even though the diffusion coefficients of individual components depend sensitively on the e-h scattering rates. Our discussions lead to new perspectives into the roles played in the single-component reduction by the electron-hole correlation in momentum space induced by scatterings and the electron-hole correlation in real space via internal static electrical field. Finally, the theory is completed by coupling the diffusion equations to the lattice temperature equation and to the effective optical polarization which in turn couples to the laser field.

Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments.

PubMed

Zhu, Tianyu; de Silva, Piotr; Van Voorhis, Troy

2018-01-09

Chemical bonding plays a central role in the description and understanding of chemistry. Many methods have been proposed to extract information about bonding from quantum chemical calculations, the majority of them resorting to molecular orbitals as basic descriptors. Here, we present a method called self-attractive Hartree (SAH) decomposition to unravel pairs of electrons directly from the electron density, which unlike molecular orbitals is a well-defined observable that can be accessed experimentally. The key idea is to partition the density into a sum of one-electron fragments that simultaneously maximize the self-repulsion and maintain regular shapes. This leads to a set of rather unusual equations in which every electron experiences self-attractive Hartree potential in addition to an external potential common for all the electrons. The resulting symmetry breaking and localization are surprisingly consistent with chemical intuition. SAH decomposition is also shown to be effective in visualization of single/multiple bonds, lone pairs, and unusual bonds due to the smooth nature of fragment densities. Furthermore, we demonstrate that it can be used to identify specific chemical bonds in molecular complexes and provides a simple and accurate electrostatic model of hydrogen bonding.

Probability density and exceedance rate functions of locally Gaussian turbulence

NASA Technical Reports Server (NTRS)

Mark, W. D.

1989-01-01

A locally Gaussian model of turbulence velocities is postulated which consists of the superposition of a slowly varying strictly Gaussian component representing slow temporal changes in the mean wind speed and a more rapidly varying locally Gaussian turbulence component possessing a temporally fluctuating local variance. Series expansions of the probability density and exceedance rate functions of the turbulence velocity model, based on Taylor's series, are derived. Comparisons of the resulting two-term approximations with measured probability density and exceedance rate functions of atmospheric turbulence velocity records show encouraging agreement, thereby confirming the consistency of the measured records with the locally Gaussian model. Explicit formulas are derived for computing all required expansion coefficients from measured turbulence records.

Strong-field ionization of Li and Be: a time-dependent density functional theory with self-interaction correction

NASA Astrophysics Data System (ADS)

Telnov, Dmitry A.; Heslar, John T.; Chu, Shih-I.

2011-11-01

In the framework of the time-dependent density functional theory, we have performed 3D calculations of multiphoton ionization of Li and Be atoms by strong near-infrared laser fields. The results for the intensity-dependent probabilities of single and double ionization are presented. We make use of the time-dependent Krieger-Li-Iafrate exchange-correlation potential with self-interaction correction (TD-KLI-SIC). Such a potential possesses an integer discontinuity which improves description of the ionization process. However, we have found that the discontinuity of the TD-KLI-SIC potential is not sufficient to reproduce characteristic feature of double ionization.

Consistency criteria for generalized Cuddeford systems

NASA Astrophysics Data System (ADS)

Ciotti, Luca; Morganti, Lucia

2010-01-01

General criteria to check the positivity of the distribution function (phase-space consistency) of stellar systems of assigned density and anisotropy profile are useful starting points in Jeans-based modelling. Here, we substantially extend previous results, and present the inversion formula and the analytical necessary and sufficient conditions for phase-space consistency of the family of multicomponent Cuddeford spherical systems: the distribution function of each density component of these systems is defined as the sum of an arbitrary number of Cuddeford distribution functions with arbitrary values of the anisotropy radius, but identical angular momentum exponent. The radial trend of anisotropy that can be realized by these models is therefore very general. As a surprising byproduct of our study, we found that the `central cusp-anisotropy theorem' (a necessary condition for consistency relating the values of the central density slope and of the anisotropy parameter) holds not only at the centre but also at all radii in consistent multicomponent generalized Cuddeford systems. This last result suggests that the so-called mass-anisotropy degeneracy could be less severe than what is sometimes feared.

Doubly self-consistent field theory of grafted polymers under simple shear in steady state.

PubMed

Suo, Tongchuan; Whitmore, Mark D

2014-03-21

We present a generalization of the numerical self-consistent mean-field theory of polymers to the case of grafted polymers under simple shear. The general theoretical framework is presented, and then applied to three different chain models: rods, Gaussian chains, and finitely extensible nonlinear elastic (FENE) chains. The approach is self-consistent at two levels. First, for any flow field, the polymer density profile and effective potential are calculated self-consistently in a manner similar to the usual self-consistent field theory of polymers, except that the calculation is inherently two-dimensional even for a laterally homogeneous system. Second, through the use of a modified Brinkman equation, the flow field and the polymer profile are made self-consistent with respect to each other. For all chain models, we find that reasonable levels of shear cause the chains to tilt, but it has very little effect on the overall thickness of the polymer layer, causing a small decrease for rods, and an increase of no more than a few percent for the Gaussian and FENE chains. Using the FENE model, we also probe the individual bond lengths, bond correlations, and bond angles along the chains, the effects of the shear on them, and the solvent and bonded stress profiles. We find that the approximations needed within the theory for the Brinkman equation affect the bonded stress, but none of the other quantities.

Testing spatial measures of alcohol outlet density with self-rated health in the Australian context: Implications for policy and practice.

PubMed

Badland, Hannah; Mavoa, Suzanne; Livingston, Michael; David, Stephanie; Giles-Corti, Billie

2016-05-01

Reducing access to alcohol is an important and cost-effective strategy for decreasing alcohol consumption and associated harm. Yet this is a less common approach to alcohol control in Australia. The aim of this research was to ascertain which alcohol outlet density spatial measures were related to long-term health outcomes, and the extent to which this differs for those living in more or less disadvantaged neighbourhoods. Existing Australian state-level spatial alcohol policies were reviewed. No appropriate spatial policies were identified; therefore, the literature was used to identify potential alcohol-related spatial measures. Spatial measures of alcohol outlet density were generated in a geographical information system and linked with health survey data drawn from 3141 adults living in metropolitan Melbourne. Logistic regression analysis was used to examine associations between alcohol outlet density measures, self-rated health and area-level disadvantage. Twelve spatial measures of alcohol outlet density were generated. Alcohol outlet density and self-rated health associations varied by area-level disadvantage. For those living in more disadvantaged areas, not having off-licenses available within 800 m, or on-licenses available within 400 m were protective of self-rated health. Local alcohol outlet density may have a more detrimental effect on self-rated health for those living in more disadvantaged neighbourhoods, compared with those living in more advantaged areas. There is a need for spatial alcohol policies to help reduce alcohol-related harm. This research proposes a set of spatial measures to generate a more consistent understanding of alcohol availability in Australia. [Badland H, Mavoa S, Livingston M, David S, Giles-Corti B. Testing spatial measures of alcohol outlet density with self-rated health in the Australian context: Implications for policy and practice. Drug Alcohol Rev 2016;35:298-306]. © 2015 Australasian Professional Society on Alcohol and other Drugs.

Electronic and optical properties of titanium nitride bulk and surfaces from first principles calculations

NASA Astrophysics Data System (ADS)

Mehmood, Faisal; Pachter, Ruth; Murphy, Neil R.; Johnson, Walter E.

2015-11-01

Prediction of the frequency-dependent dielectric function of thin films poses computational challenges, and at the same time experimental characterization by spectroscopic ellipsometry remains difficult to interpret because of changes in stoichiometry and surface morphology, temperature, thickness of the film, or substrate. In this work, we report calculations for titanium nitride (TiN), a promising material for plasmonic applications because of less loss and other practical advantages compared to noble metals. We investigated structural, electronic, and optical properties of stoichiometric bulk TiN, as well as of the TiN(100), TiN(110), and TiN(111) outermost surfaces. Density functional theory (DFT) and many-body GW methods (Green's (G) function-based approximation with screened Coulomb interaction (W)) were used, ranging from G0W0, GW0 to partially self-consistent sc-GW0, as well as the GW-BSE (Bethe-Salpeter equation) and time-dependent DFT (TDDFT) methods for prediction of the optical properties. Structural parameters and the band structure for bulk TiN were shown to be consistent with previous work. Calculated dielectric functions, plasma frequencies, reflectivity, and the electron energy loss spectrum demonstrated consistency with experiment at the GW0-BSE level. Deviations from experimental data are expected due to varying experimental conditions. Comparison of our results to spectroscopic ellipsometry data for realistic nanostructures has shown that although TDDFT may provide a computationally feasible level of theory in evaluation of the dielectric function, application is subject to validation with GW-BSE calculations.

Functional DNA-Containing Nanomaterials: Cellular Applications in Biosensing, Imaging, and Targeted Therapy

PubMed Central

2015-01-01

Conspectus DNA performs a vital function as a carrier of genetic code, but in the field of nanotechnology, DNA molecules can catalyze chemical reactions in the cell, that is, DNAzymes, or bind with target-specific ligands, that is, aptamers. These functional DNAs with different modifications have been developed for sensing, imaging, and therapeutic systems. Thus, functional DNAs hold great promise for future applications in nanotechnology and bioanalysis. However, these functional DNAs face challenges, especially in the field of biomedicine. For example, functional DNAs typically require the use of cationic transfection reagents to realize cellular uptake. Such reagents enter the cells, increasing the difficulty of performing bioassays in vivo and potentially damaging the cell’s nucleus. To address this obstacle, nanomaterials, such as metallic, carbon, silica, or magnetic materials, have been utilized as DNA carriers or assistants. In this Account, we describe selected examples of functional DNA-containing nanomaterials and their applications from our recent research and those of others. As models, we have chosen to highlight DNA/nanomaterial complexes consisting of gold nanoparticles, graphene oxides, and aptamer–micelles, and we illustrate the potential of such complexes in biosensing, imaging, and medical diagnostics. Under proper conditions, multiple ligand–receptor interactions, decreased steric hindrance, and increased surface roughness can be achieved from a high density of DNA that is bound to the surface of nanomaterials, resulting in a higher affinity for complementary DNA and other targets. In addition, this high density of DNA causes a high local salt concentration and negative charge density, which can prevent DNA degradation. For example, DNAzymes assembled on gold nanoparticles can effectively catalyze chemical reactions even in living cells. And it has been confirmed that DNA–nanomaterial complexes can enter cells more easily than free single-stranded DNA. Nanomaterials can be designed and synthesized in needed sizes and shapes, and they possess unique chemical and physical properties, which make them useful as DNA carriers or assistants, excellent signal reporters, transducers, and amplifiers. When nanomaterials are combined with functional DNAs to create novel assay platforms, highly sensitive biosensing and high-resolution imaging result. For example, gold nanoparticles and graphene oxides can quench fluorescence efficiently to achieve low background and effectively increase the signal-to-background ratio. Meanwhile, gold nanoparticles themselves can be colorimetric reporters because of their different optical absorptions between monodispersion and aggregation. DNA self-assembled nanomaterials contain several properties of both DNA and nanomaterials. Compared with DNA–nanomaterial complexes, DNA self-assembled nanomaterials more closely resemble living beings, and therefore they have lower cytotoxicity at high concentrations. Functional DNA self-assemblies also have high density of DNA for multivalent reaction and three-dimensional nanostructures for cell uptake. Now and in the future, we envision the use of DNA bases in making designer molecules for many challenging applications confronting chemists. With the further development of artificial DNA bases using smart organic synthesis, DNA macromolecules based on elegant molecular assembly approaches are expected to achieve great diversity, additional versatility, and advanced functions. PMID:24780000

Functional DNA-containing nanomaterials: cellular applications in biosensing, imaging, and targeted therapy.

PubMed

Liang, Hao; Zhang, Xiao-Bing; Lv, Yifan; Gong, Liang; Wang, Ruowen; Zhu, Xiaoyan; Yang, Ronghua; Tan, Weihong

2014-06-17

CONSPECTUS: DNA performs a vital function as a carrier of genetic code, but in the field of nanotechnology, DNA molecules can catalyze chemical reactions in the cell, that is, DNAzymes, or bind with target-specific ligands, that is, aptamers. These functional DNAs with different modifications have been developed for sensing, imaging, and therapeutic systems. Thus, functional DNAs hold great promise for future applications in nanotechnology and bioanalysis. However, these functional DNAs face challenges, especially in the field of biomedicine. For example, functional DNAs typically require the use of cationic transfection reagents to realize cellular uptake. Such reagents enter the cells, increasing the difficulty of performing bioassays in vivo and potentially damaging the cell's nucleus. To address this obstacle, nanomaterials, such as metallic, carbon, silica, or magnetic materials, have been utilized as DNA carriers or assistants. In this Account, we describe selected examples of functional DNA-containing nanomaterials and their applications from our recent research and those of others. As models, we have chosen to highlight DNA/nanomaterial complexes consisting of gold nanoparticles, graphene oxides, and aptamer-micelles, and we illustrate the potential of such complexes in biosensing, imaging, and medical diagnostics. Under proper conditions, multiple ligand-receptor interactions, decreased steric hindrance, and increased surface roughness can be achieved from a high density of DNA that is bound to the surface of nanomaterials, resulting in a higher affinity for complementary DNA and other targets. In addition, this high density of DNA causes a high local salt concentration and negative charge density, which can prevent DNA degradation. For example, DNAzymes assembled on gold nanoparticles can effectively catalyze chemical reactions even in living cells. And it has been confirmed that DNA-nanomaterial complexes can enter cells more easily than free single-stranded DNA. Nanomaterials can be designed and synthesized in needed sizes and shapes, and they possess unique chemical and physical properties, which make them useful as DNA carriers or assistants, excellent signal reporters, transducers, and amplifiers. When nanomaterials are combined with functional DNAs to create novel assay platforms, highly sensitive biosensing and high-resolution imaging result. For example, gold nanoparticles and graphene oxides can quench fluorescence efficiently to achieve low background and effectively increase the signal-to-background ratio. Meanwhile, gold nanoparticles themselves can be colorimetric reporters because of their different optical absorptions between monodispersion and aggregation. DNA self-assembled nanomaterials contain several properties of both DNA and nanomaterials. Compared with DNA-nanomaterial complexes, DNA self-assembled nanomaterials more closely resemble living beings, and therefore they have lower cytotoxicity at high concentrations. Functional DNA self-assemblies also have high density of DNA for multivalent reaction and three-dimensional nanostructures for cell uptake. Now and in the future, we envision the use of DNA bases in making designer molecules for many challenging applications confronting chemists. With the further development of artificial DNA bases using smart organic synthesis, DNA macromolecules based on elegant molecular assembly approaches are expected to achieve great diversity, additional versatility, and advanced functions.

The Attentional Demand of Automobile Driving Revisited: Occlusion Distance as a Function of Task-Relevant Event Density in Realistic Driving Scenarios.

PubMed

Kujala, Tuomo; Mäkelä, Jakke; Kotilainen, Ilkka; Tokkonen, Timo

2016-02-01

We studied the utility of occlusion distance as a function of task-relevant event density in realistic traffic scenarios with self-controlled speed. The visual occlusion technique is an established method for assessing visual demands of driving. However, occlusion time is not a highly informative measure of environmental task-relevant event density in self-paced driving scenarios because it partials out the effects of changes in driving speed. Self-determined occlusion times and distances of 97 drivers with varying backgrounds were analyzed in driving scenarios simulating real Finnish suburban and highway traffic environments with self-determined vehicle speed. Occlusion distances varied systematically with the expected environmental demands of the manipulated driving scenarios whereas the distributions of occlusion times remained more static across the scenarios. Systematic individual differences in the preferred occlusion distances were observed. More experienced drivers achieved better lane-keeping accuracy than inexperienced drivers with similar occlusion distances; however, driving experience was unexpectedly not a major factor for the preferred occlusion distances. Occlusion distance seems to be an informative measure for assessing task-relevant event density in realistic traffic scenarios with self-controlled speed. Occlusion time measures the visual demand of driving as the task-relevant event rate in time intervals, whereas occlusion distance measures the experienced task-relevant event density in distance intervals. The findings can be utilized in context-aware distraction mitigation systems, human-automated vehicle interaction, road speed prediction and design, as well as in the testing of visual in-vehicle tasks for inappropriate in-vehicle glancing behaviors in any dynamic traffic scenario for which appropriate individual occlusion distances can be defined. © 2015, Human Factors and Ergonomics Society.

Sapwood area ofPinus contorta stands as a function of mean size and density.

PubMed

Long, James N; Dean, Thomas J

1986-09-01

An indirect test of the relationship between leaf area and the combination of mean size and density is made in stands of lodgepole pine (Pinus contorta Dougl.). Total sapwood cross-sectional area of these stands is a function of the product of density and mean diameter raised to an exponent of about 1.6. Results from other studies, representing four species, suggest that this relationship between sapwood area and the combination of mean size and density may be general. The implications of the relationship are discussed in the context of evapotranspiration, competition and self-thinning.

Liquid 4He at Zero Temperature and the STLS Scheme

NASA Astrophysics Data System (ADS)

Doroudi, A.

2007-07-01

Within the framework of the self-consistent scheme proposed by Singwi, Tosi, Land and Sjölander (STLS) for an interacting system we study the properties of superfluid liquid 4He. By employing the Aziz potential (HFD-B) as the interaction potential between helium atoms, we have calculated the static structure factor, the pair-correlation function, the elementary excitation spectrum and the effective two-body interaction as a function of wave-vector, for different densities. Our results show considerable improvement over the Ng-Singwi’s model potential of a hard core plus an attractive tail and are comparable with experimental data. We have compared our results with experimental data and with the results of some theoretical models. Agreement between our results and the experimental data for the static structure factor for the small k values is fairly good.

Electronic transport properties of a quinone-based molecular switch

NASA Astrophysics Data System (ADS)

Zheng, Ya-Peng; Bian, Bao-An; Yuan, Pei-Pei

2016-09-01

In this paper, we carried out first-principles calculations based on density functional theory and non-equilibrium Green's function to investigate the electronic transport properties of a quinone-based molecule sandwiched between two Au electrodes. The molecular switch can be reversibly switched between the reduced hydroquinone (HQ) and oxidized quinone (Q) states via redox reactions. The switching behavior of two forms is analyzed through their I- V curves, transmission spectra and molecular projected self-consistent Hamiltonian at zero bias. Then we discuss the transmission spectra of the HQ and Q forms at different bias, and explain the oscillation of current according to the transmission eigenstates of LUMO energy level for Q form. The results suggest that this kind of a quinone-based molecule is usable as one of the good candidates for redox-controlled molecular switches.

Nonequilibrium evolution of scalar fields in FRW cosmologies

NASA Astrophysics Data System (ADS)

Boyanovsky, D.; de Vega, H. J.; Holman, R.

1994-03-01

We derive the effective equations for the out of equilibrium time evolution of the order parameter and the fluctuations of a scalar field theory in spatially flat FRW cosmologies. The calculation is performed both to one loop and in a nonperturbative, self-consistent Hartree approximation. The method consists of evolving an initial functional thermal density matrix in time and is suitable for studying phase transitions out of equilibrium. The renormalization aspects are studied in detail and we find that the counterterms depend on the initial state. We investigate the high temperature expansion and show that it breaks down at long times. We also obtain the time evolution of the initial Boltzmann distribution functions, and argue that to one-loop order or in the Hartree approximation the time evolved state is a ``squeezed'' state. We illustrate the departure from thermal equilibrium by numerically studying the case of a free massive scalar field in de Sitter and radiation-dominated cosmologies. It is found that a suitably defined nonequilibrium entropy per mode increases linearly with comoving time in a de Sitter cosmology, whereas it is not a monotonically increasing function in the radiation-dominated case.

The effects of temperature dependent recombination rates on performance of InGaN/GaN blue superluminescent light emitting diodes

NASA Astrophysics Data System (ADS)

Moslehi Milani, N.; Mohadesi, V.; Asgari, A.

2015-07-01

The effects of temperature dependent radiative and nonradiative recombination (Shockley-Read-Hall, spontaneous radiative, and Auger coefficients) on the spectral and power characteristics of a blue multiple quantum well (MQW) superluminescent light emitting diode (SLD or SLED) have been studied. The study is based on the rate equations model, where three rate equations corresponding to MQW active region, separate confinement heterostructure (SCH) layer, and spectral density of optical power are solved self-consistently with no k-selection energy dependent gain and quasi-Fermi level functions at steady state. We have taken into account the temperature effects on Shockley-Read-Hall (SRH), spontaneous radiative, and Auger recombination in the rate equations and have investigated the effects of temperature rising from 300 K to 375 K at a fixed current density. We examine this procedure for a moderate current density and interpret the spectral radiation power and light output power diagrams. The investigation reveals that the main loss due to temperature is related to Auger coefficient.

Calibration of the Oscillating Screen Viscometer

NASA Technical Reports Server (NTRS)

Berg, Robert F.; Moldover, Michael R.

1993-01-01

We have devised a calibration procedure for the oscillating screen viscometer which can provide the accuracy needed for the flight measurement of viscosity near the liquid-vapor critical point of xenon. The procedure, which makes use of the viscometer's wide bandwidth and hydrodynamic similarity, allows the viscometer to be self-calibrating. To demonstrate the validity of this procedure we measured the oscillator's transfer function under a wide variety of conditions. We obtained data using CO2 at temperatures spanning a temperature range of 35 K and densities varying by a factor of 165, thereby encountering viscosity variations as great as 50%. In contrast the flight experiment will be performed over a temperature range of 29 K and at only a single density, and the viscosity is expected to change by less than 40%. The measurements show that, after excluding data above 10 Hz (where frequency-dependent corrections are poorly modeled) and making a plausible adjustment to the viscosity value used at high density, the viscometer's behavior is fully consistent with the use of hydrodynamic similarity for calibration. Achieving this agreement required understanding a 1% anelastic effect present in the oscillator's torsion fiber.

Ab-initio Electronic, Transport and Related Properties of Zinc Blende Boron Arsenide (zb-BAs)

NASA Astrophysics Data System (ADS)

Nwigboji, Ifeanyi H.; Malozovsky, Yuriy; Bagayoko, Diola

We present results from ab-initio, self-consistent density functional theory (DFT) calculations of electronic, transport, and bulk properties of zinc blende boron arsenide (zb-BAs). We utilized a local density approximation (LDA) potential and the linear combination of atomic orbital (LCAO) formalism. Our computational technique follows the Bagayoko, Zhao, and Williams method, as enhanced by Ekuma and Franklin. Our results include electronic energy bands, densities of states, and effective masses. We explain the agreement between these findings, including the indirect band gap, and available, corresponding, experimental ones. This work confirms the capability of DFT to describe accurately properties of materials, provided the computations adhere to the conditions of validity of DFT [AIP Advances, 4, 127104 (2014)]. Acknowledgments: This work was funded in part by the National Science Foundation (NSF) and the Louisiana Board of Regents, through LASiGMA [Award Nos. EPS- 1003897, NSF (2010-15)-RII-SUBR] and NSF HRD-1002541, the US Department of Energy - National, Nuclear Security Administration (NNSA) (Award No. DE- NA0002630), LaSPACE, and LONI-SUBR.

Relative elemental abundance and heating constraints determined for the solar corona from SERTS measurements

NASA Technical Reports Server (NTRS)

Falconer, David A.

1994-01-01

Intensities of EUV spectral lines were measured as a function of radius off the solar limb by two flights of Goddard's Solar EUV Rocket Telescope and Spectrograph (SERTS) for three quiet sun regions. The density scale height, line-ratio densities, line-ratio temperatures, and emission measures were determined. The line-ratio temperature determined from the ionization balances of Arnaud and Rothenflug (1985) were more self-consistent than the line-ratio temperatures obtained from the values of Arnaud and Raymond (1992). Limits on the filling factor were determined from the emission measure and the line-ratio densities for all three regions. The relative abundances of silicon, aluminum, and chromium to iron were determined. Results did agree with standard coronal relative elemental abundances for one observation, but did not agree for another. Aluminum was overabundant while silicon was underabundant. Heating was required above 1.15 solar radii for all three regions studied. For two regions, local nonconductive heating is needed for any filling factor, and in all three regions for filling factor of 0.1.

Research on the self-absorption corrections for PGNAA of large samples

NASA Astrophysics Data System (ADS)

Yang, Jian-Bo; Liu, Zhi; Chang, Kang; Li, Rui

2017-02-01

When a large sample is analysed with the prompt gamma neutron activation analysis (PGNAA) neutron self-shielding and gamma self-absorption affect the accuracy, the correction method for the detection efficiency of the relative H of each element in a large sample is described. The influences of the thickness and density of the cement samples on the H detection efficiency, as well as the impurities Fe2O3 and SiO2 on the prompt γ ray yield for each element in the cement samples, were studied. The phase functions for Ca, Fe, and Si on H with changes in sample thickness and density were provided to avoid complicated procedures for preparing the corresponding density or thickness scale for measuring samples under each density or thickness value and to present a simplified method for the measurement efficiency scale for prompt-gamma neutron activation analysis.

Assembling new technologies at the interface of materials science and biology

NASA Astrophysics Data System (ADS)

Stendahl, John C.

Molecular self-assembly can be used to construct advanced materials by taking cues from nature and harnessing noncovalent interactions. This bottom-up approach affords molecular level precision that can cultivate pathways to improved materials function. The graduate research presented in this thesis integrates molecular self-assembly with traditional concepts in chemistry and materials science, with the ultimate goal of developing innovative solutions in technology and medicine. In the field of polymer engineering, self-assembly was used to create supramolecular nanoribbons that, when incorporated into polystyrene, modify its microstructure and significantly enhance its toughness and ductility. In medicine, self-assembly was used to create ordered, chemically functional materials to improve interactions with cells and other constituents of the biological environment. One system that was investigated is based on a triblock molecule in which cholesterol is connected to a lysine dendron by a flexible oligo-(L-lactic acid) spacer. These molecules self-assemble into polar surface coatings on fibrous poly(L-lactic acid) scaffolds that improve the scaffold's wettability and increase its retention of cells during seeding. Another self-assembling system that was investigated for biomedical applications is a family of molecules referred to as peptide amphiphiles (PA's). PA's consist of hydrophobic alkyl tails connected to short, hydrophilic peptides that incorporate biological signaling epitopes. These molecules spontaneously assemble into networks of well-defined nanofibers in aqueous environments, with the signaling epitopes presented in high density on the nanofiber exteriors. Nanofiber assembly is triggered by charge screening on the peptides and is able to produce self-supporting gels in concentrations of less than 1.0 wt.-%. The assembly process and mechanical properties of PA gels was investigated in detail with vibrational spectroscopy and oscillatory rheology. PA nanofibers were used in conjunction with fibrous poly(L-lactic acid] fabrics to create chemically functional scaffolds to facilitate islet cell transplantation. In transplant studies in diabetic mice, the use of scaffolds for islet delivery was shown to significantly improve transplant outcomes over free islet injections. Together, these studies illustrate that molecular self-assembly can be used to create functional materials for a variety of applications. These materials utilize noncovalent interactions to produce supramolecular structures that have important impacts on properties.

Polarized photon scattering off 52Cr: Determining the parity of J =1 states

NASA Astrophysics Data System (ADS)

Krishichayan, Bhike, Megha; Tornow, W.; Rusev, G.; Tonchev, A. P.; Tsoneva, N.; Lenske, H.

2015-04-01

The photoresponse of 52Cr has been investigated in the energy range of 5.0-9.5 MeV using the photon scattering technique at the HI γ S facility of TUNL to complement previous work with unpolarized bremsstrahlung photon beams at the Darmstadt linear electron accelerator. The unambiguous parity determinations of the observed J =1 states provides the basis needed to better understand the structure of E 1 and M 1 excitations. Theoretical calculations using the quasiparticle phonon model incorporating self-consistent energy-density functional theory were performed to investigate the fragmentation pattern of the dipole strength below and around the neutron-emission threshold. These results compare very well with the experimental values.

High-throughput ab-initio dilute solute diffusion database

PubMed Central

Wu, Henry; Mayeshiba, Tam; Morgan, Dane

2016-01-01

We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world. PMID:27434308

Benford's law and the FSD distribution of economic behavioral micro data

NASA Astrophysics Data System (ADS)

Villas-Boas, Sofia B.; Fu, Qiuzi; Judge, George

2017-11-01

In this paper, we focus on the first significant digit (FSD) distribution of European micro income data and use information theoretic-entropy based methods to investigate the degree to which Benford's FSD law is consistent with the nature of these economic behavioral systems. We demonstrate that Benford's law is not an empirical phenomenon that occurs only in important distributions in physical statistics, but that it also arises in self-organizing dynamic economic behavioral systems. The empirical likelihood member of the minimum divergence-entropy family, is used to recover country based income FSD probability density functions and to demonstrate the implications of using a Benford prior reference distribution in economic behavioral system information recovery.

Non-linear eigensolver-based alternative to traditional SCF methods

NASA Astrophysics Data System (ADS)

Gavin, B.; Polizzi, E.

2013-05-01

The self-consistent procedure in electronic structure calculations is revisited using a highly efficient and robust algorithm for solving the non-linear eigenvector problem, i.e., H({ψ})ψ = Eψ. This new scheme is derived from a generalization of the FEAST eigenvalue algorithm to account for the non-linearity of the Hamiltonian with the occupied eigenvectors. Using a series of numerical examples and the density functional theory-Kohn/Sham model, it will be shown that our approach can outperform the traditional SCF mixing-scheme techniques by providing a higher converge rate, convergence to the correct solution regardless of the choice of the initial guess, and a significant reduction of the eigenvalue solve time in simulations.

Ab initio simulations of the dynamic ion structure factor of warm dense lithium

DOE PAGES

Witte, B. B. L.; Shihab, M.; Glenzer, S. H.; ...

2017-04-06

Here, we present molecular dynamics simulations based on finite-temperature density functional theory that determine self-consistently the dynamic ion structure factor and the electronic form factor in lithium. Our comprehensive data set allows for the calculation of the dispersion relation for collective excitations, the calculation of the sound velocity, and the determination of the ion feature from the total electronic form factor and the ion structure factor. The results are compared with available experimental x-ray and neutron scattering data. Good agreement is found for both the liquid metal and warm dense matter domain. Finally, we study the impact of possible targetmore » inhomogeneities on x-ray scattering spectra.« less

Ab initio simulations of the dynamic ion structure factor of warm dense lithium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Witte, B. B. L.; Shihab, M.; Glenzer, S. H.

Here, we present molecular dynamics simulations based on finite-temperature density functional theory that determine self-consistently the dynamic ion structure factor and the electronic form factor in lithium. Our comprehensive data set allows for the calculation of the dispersion relation for collective excitations, the calculation of the sound velocity, and the determination of the ion feature from the total electronic form factor and the ion structure factor. The results are compared with available experimental x-ray and neutron scattering data. Good agreement is found for both the liquid metal and warm dense matter domain. Finally, we study the impact of possible targetmore » inhomogeneities on x-ray scattering spectra.« less

Solving the Self-Interaction Problem in Kohn-Sham Density Functional Theory. Application to Atoms

DOE PAGES

Daene, M.; Gonis, A.; Nicholson, D. M.; ...

2014-10-14

Previously, we proposed a computational methodology that addresses the elimination of the self-interaction error from the Kohn–Sham formulation of the density functional theory. We demonstrated how the exchange potential can be obtained, and presented results of calculations for atomic systems up to Kr carried out within a Cartesian coordinate system. In our paper, we provide complete details of this self-interaction free method formulated in spherical coordinates based on the explicit equidensity basis ansatz. We also prove analytically that derivatives obtained using this method satisfy the Virial theorem for spherical orbitals, where the problem can be reduced to one dimension. Wemore » present the results of calculations of ground-state energies of atomic systems throughout the periodic table carried out within the exchange-only mode.« less

DFT calculations on molecular structure, spectral analysis, multiple interactions, reactivity, NLO property and molecular docking study of flavanol-2,4-dinitrophenylhydrazone

NASA Astrophysics Data System (ADS)

Singh, Ravindra Kumar; Singh, Ashok Kumar

2017-02-01

A new flavanol-2,4-dinitrophenylhydrazone (FDNP) was synthesized and its structure was confirmed by FT-IR, FT-Raman, 1H NMR, mass spectrometry and elemental analysis. All quantum chemical calculations were carried out at level of density functional theory (DFT) with B3LYP functional using 6-311++ G (d,p) basis atomic set. UV-Vis absorption spectra for the singlet-singlet transition computed for fully optimized ground state geometry using Time-Dependent-Density Functional Theory (TD-DFT) with CAM-B3LYP functional was found to be in consistent with that of experimental findings. Analysis of vibrational (FT-IR and FT-Raman) spectrum and their assignments has been done by computing Potential Energy Distribution (PED) using Gar2ped. HOMO-LUMO analysis was performed and reactivity descriptors were calculated. Calculated global electrophilicity index (ω = 7.986 eV) shows molecule to be a strong electrophile. 1H NMR chemical shift calculated with the help of gauge-including atomic orbital (GIAO) approach shows agreement with experimental data. Various intramolecular interactions were analysed by AIM approach. DFT computed total first static hyperpolarizability (β0 = 189.03 × 10-30 esu) indicates that title molecule can be used as attractive future NLO material. Solvent induced effects on the NLO properties studied by using self-consistent reaction field (SCRF) method shows that β0 value increases with increase in solvent polarity. To study the thermal behaviour of title molecule, thermodynamic properties such as heat capacity, entropy and enthalpy change at various temperatures have been calculated and reported. Molecular docking results suggests title molecule to be a potential kinase inhibitor and might be used in future for designing of new anticancer drug.

Langmuir turbulence driven by beams in solar wind plasmas with long wavelength density fluctuations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krafft, C., E-mail: catherine.krafft@u-psud.fr; Universite´ Paris Sud, 91405 Orsay Cedex; Volokitin, A., E-mail: a.volokitin@mail.ru

2016-03-25

The self-consistent evolution of Langmuir turbulence generated by electron beams in solar wind plasmas with density inhomogeneities is calculated by numerical simulations based on a 1D Hamiltonian model. It is shown, owing to numerical simulations performed with parameters relevant to type III solar bursts’ conditions at 1 AU, that the presence of long-wavelength random density fluctuations of sufficiently large average level crucially modifies the well-known process of beam interaction with Langmuir waves in homogeneous plasmas.

Dense simple plasmas as high-temperature liquid simple metals

NASA Technical Reports Server (NTRS)

Perrot, F.

1990-01-01

The thermodynamic properties of dense plasmas considered as high-temperature liquid metals are studied. An attempt is made to show that the neutral pseudoatom picture of liquid simple metals may be extended for describing plasmas in ranges of densities and temperatures where their electronic structure remains 'simple'. The primary features of the model when applied to plasmas include the temperature-dependent self-consistent calculation of the electron charge density and the determination of a density and temperature-dependent ionization state.

Self-consistent discharge growing model of helicon plasma

NASA Astrophysics Data System (ADS)

Isayama, Shogo; Hada, Tohru; Shinohara, Shunjiro; Tanikawa, Takao

2015-11-01

Helicon plasma is a high-density and low-temperature plasma generated by the electromagnetic (Helicon) wave excited in the plasma. It is thought to be useful for various applications including electric thrusters. Physics of helicon plasma production involves such fundamental processes as the wave propagation (dispersion relation), collisional and non-collisional wave damping, plasma heating, ionization/recombination of neutral particles, and modification of the dispersion relation by newly ionized plasma. There remain a number of unsolved physical issues such as, how the Helicon and the TG modes influence the plasma density, electron temperature and their spatial profiles. While the Helicon mode is absorbed in the bulk plasma, the TG mode is mostly absorbed near the edge of the plasma. The local power deposition in the helicon plasma is mostly balanced by collisional loss. This local power balance can give rise to the inhomogeneous electron temperature profile that leads to time evolution of density profile and dispersion relation. In our study, we construct a self-consistent model of the discharge evolution that includes the wave excitation, electron heat transfer, and diffusion of charged particles.

Largely reduced grid densities in a vibrational self-consistent field treatment do not significantly impact the resultingwavenumbers.

PubMed

Lutz, Oliver M D; Rode, Bernd M; Bonn, Günther K; Huck, Christian W

2014-12-17

Especially for larger molecules relevant to life sciences, vibrational self-consistent field (VSCF) calculations can become unmanageably demanding even when only first and second order potential coupling terms are considered. This paper investigates to what extent the grid density of the VSCF's underlying potential energy surface can be reduced without sacrificing accuracy of the resulting wavenumbers. Including single-mode and pair contributions, a reduction to eight points per mode did not introduce a significant deviation but improved the computational efficiency by a factor of four. A mean unsigned deviation of 1.3% from the experiment could be maintained for the fifteen molecules under investigation and the approach was found to be applicable to rigid, semi-rigid and soft vibrational problems likewise. Deprotonated phosphoserine, stabilized by two intramolecular hydrogen bonds, was investigated as an exemplary application.

A Redshift Survey of IRAS Galaxies. II. Methods for Determining Self-consistent Velocity and Density Fields: Erratum

NASA Astrophysics Data System (ADS)

Yahil, Amos; Strauss, Michael A.; Davis, Marc; Huchra, John P.

1991-11-01

In the paper, "A Redshift Survey of IRAS Galaxies. II. Methods for Determining Self-consistent Velocity and Density Fields" by Amos Yahil, Michael A. Strauss, Marc Davis, and John P. Huchra (ApJ, 372,380 [1991]), Figures 14 and 15 were presented out of order, with their legends reversed. Thus, the figure at the bottom of page 391 is Figure 15, and should have the legend: "Fig. 15.-As in Fig. 13, for the method 3 results." The figure at the top of page 392 is Figure 14, and should have the legend: "Fig. 14.-Plot in Galactic coordinates of the quantity V_diff_ for galaxies within 3000 km s^-1^ of the LG. The symbol size is proportional to V_diff_ - 400 km s^-1^, which measures the deviation of the redshift- distance relation along the line of sight to that galaxy from pure Hubble flow."

Unmasking the masked Universe: the 2M++ catalogue through Bayesian eyes

NASA Astrophysics Data System (ADS)

Lavaux, Guilhem; Jasche, Jens

2016-01-01

This work describes a full Bayesian analysis of the Nearby Universe as traced by galaxies of the 2M++ survey. The analysis is run in two sequential steps. The first step self-consistently derives the luminosity-dependent galaxy biases, the power spectrum of matter fluctuations and matter density fields within a Gaussian statistic approximation. The second step makes a detailed analysis of the three-dimensional large-scale structures, assuming a fixed bias model and a fixed cosmology. This second step allows for the reconstruction of both the final density field and the initial conditions at z = 1000 assuming a fixed bias model. From these, we derive fields that self-consistently extrapolate the observed large-scale structures. We give two examples of these extrapolation and their utility for the detection of structures: the visibility of the Sloan Great Wall, and the detection and characterization of the Local Void using DIVA, a Lagrangian based technique to classify structures.

Complex polarization propagator approach in the restricted open-shell, self-consistent field approximation: the near K-edge X-ray absorption fine structure spectra of allyl and copper phthalocyanine.

PubMed

Linares, Mathieu; Stafström, Sven; Rinkevicius, Zilvinas; Ågren, Hans; Norman, Patrick

2011-05-12

A presentation of the complex polarization propagator in the restricted open-shell self-consistent field approximation is given. It rests on a formulation of a resonant-convergent, first-order polarization propagator approach that makes it possible to directly calculate the X-ray absorption cross section at a particular frequency without explicitly addressing the excited states. The quality of the predicted X-ray spectra relates only to the type of density functional applied without any separate treatment of dynamical relaxation effects. The method is applied to the calculation of the near K-edge X-ray absorption fine structure spectra of allyl and copper phthalocyanine. Comparison is made between the spectra of the radicals and those of the corresponding cations and anions to assess the effect of the increase of electron charge in the frontier orbital. The method offers the possibility for unique assignment of symmetry-independent atoms. The overall excellent spectral agreement motivates the application of the method as a routine precise tool for analyzing X-ray absorption of large systems of technological interest.

Accelerated ions and self-excited Alfvén waves at the Earth's bow shock

NASA Astrophysics Data System (ADS)

Berezhko, E. G.; Taneev, S. N.; Trattner, K. J.

2011-07-01

The diffuse energetic ion event and related Alfvén waves upstream of the Earth's bow shock, measured by AMPTE/IRM satellite on 29 September 1984, 06:42-07:22 UT, was studied using a self-consistent quasi-linear theory of ion diffusive shock acceleration and associated Alfvén wave generation. The wave energy density satisfies a wave kinetic equation, and the ion distribution function satisfies the diffusive transport equation. These coupled equations are solved numerically, and calculated ion and wave spectra are compared with observations. It is shown that calculated steady state ion and Alfvén wave spectra are established during the time period of about 1000 s. Alfvén waves excited by accelerated ions are confined within the frequency range (10-2 to 1) Hz, and their spectral peak with the wave amplitude δB ≈ B comparable to the interplanetary magnetic field value B corresponds to the frequency 2 × 10-2 Hz. The high-frequency part of the wave spectrum undergoes absorption by thermal protons. It is shown that the observed ion spectra and the associated Alfvén wave spectra are consistent with the theoretical prediction.

Adsorption and oligomerization of 1,3-phenylene diisocyanide on Au(111)

DOE PAGES

Kestell, John; Walker, Joshua; Bai, Yun; ...

2016-04-18

The adsorption and self-assembly of 1,3-phenylene diisocyanide (1,3-PDI) are studied on Au(111) using reflection–adsorption infrared spectroscopy (RAIRS), scanning tunneling microscopy (STM), and temperature-programmed desorption (TPD) supplemented by density functional theory (DFT) calculations and the results compared with the structures formed from 1,4-PDI where it assembled to form –(Au–PDI)– oligomer chains that incorporate gold adatoms. The infrared spectra display a single isocyanide feature consistent with the isocyanide binding to gold adatoms, while DFT calculations confirm that isocyanide binding to gold adatoms is more energetically favorable than binding to the surface. STM images show that 1,3-PDI forms zigzag chains containing hairpin bendsmore » that cause the chains to double back on each other, consistent with the 120° angle between the isocyanide groups. Hexagonal structural motifs are also observed that are proposed to be due to the self-assembly of three isocyanides as well as small structures that are assigned to 1,3-PDI dimers. Furthermore, the results suggest that the formation of gold-containing oligomers from isocyanide-containing molecules is a general phenomenon.« less

The effect of particle size on the morphology and thermodynamics of diblock copolymer/tethered-particle membranes.

PubMed

Zhang, Bo; Edwards, Brian J

2015-06-07

A combination of self-consistent field theory and density functional theory was used to examine the effect of particle size on the stable, 3-dimensional equilibrium morphologies formed by diblock copolymers with a tethered nanoparticle attached either between the two blocks or at the end of one of the blocks. Particle size was varied between one and four tenths of the radius of gyration of the diblock polymer chain for neutral particles as well as those either favoring or disfavoring segments of the copolymer blocks. Phase diagrams were constructed and analyzed in terms of thermodynamic diagrams to understand the physics associated with the molecular-level self-assembly processes. Typical morphologies were observed, such as lamellar, spheroidal, cylindrical, gyroidal, and perforated lamellar, with the primary concentration region of the tethered particles being influenced heavily by particle size and tethering location, strength of the particle-segment energetic interactions, chain length, and copolymer radius of gyration. The effect of the simulation box size on the observed morphology and system thermodynamics was also investigated, indicating possible effects of confinement upon the system self-assembly processes.

Development of the Nuclear-Electronic Orbital Approach and Applications to Ionic Liquids and Tunneling Processes

DTIC Science & Technology

2010-02-24

electronic Schrodinger equation . In previous grant cycles, we implemented the NEO approach at the Hartree-Fock (NEO-HF),13 configuration interaction...electronic and nuclear molecular orbitals. The resulting electronic and nuclear Hartree-Fock-Roothaan equations are solved iteratively until self...directly into the standard Hartree- Fock-Roothaan equations , which are solved iteratively to self-consistency. The density matrix representation

Self-Consistent Magnetosphere-Ionosphere Coupling and Associated Plasma Energization Processes

NASA Technical Reports Server (NTRS)

Khazanov, G. V.; Six, N. Frank (Technical Monitor)

2002-01-01

Magnetosphere-Ionosphere (MI) coupling and associated with this process electron and ion energization processes have interested scientists for decades and, in spite of experimental and theoretical research efforts, are still ones of the least well known dynamic processes in space plasma physics. The reason for this is that the numerous physical processes associated with MI coupling occur over multiple spatial lengths and temporal scales. One typical example of MI coupling is large scale ring current (RC) electrodynamic coupling that includes calculation of the magnetospheric electric field that is consistent with the ring current (RC) distribution. A general scheme for numerical simulation of such large-scale magnetosphere-ionosphere coupling processes has been presented earlier in many works. The mathematical formulation of these models are based on "modified frozen-in flux theorem" for an ensemble of adiabatically drifting particles in the magnetosphere. By tracking the flow of particles through the inner magnetosphere, the bounce-averaged phase space density of the hot ions and electrons can be reconstructed and the magnetospheric electric field can be calculated such that it is consistent with the particle distribution in the magnetosphere. The new a self-consistent ring current model has been developed that couples electron and ion magnetospheric dynamics with calculation of electric field. Two new features were taken into account in addition to the RC ions, we solve an electron kinetic equation in our model, self-consistently including these results in the solution. Second, using different analytical relationships, we calculate the height integrated ionospheric conductances as the function of precipitated high energy magnetospheric electrons and ions as produced by our model. This results in fundamental changes to the electric potential pattern in the inner magnetosphere, with a smaller Alfven boundary than previous potential formulations would predict but one consistent with recent satellite observations. This leads to deeper penetration of the plasma sheet ions and electrons into the inner magnetosphere and more effective ring current ions and electron energization.

Galaxy clusters and cold dark matter - A low-density unbiased universe?

NASA Technical Reports Server (NTRS)

Bahcall, Neta A.; Cen, Renyue

1992-01-01

Large-scale simulations of a universe dominated by cold dark matter (CDM) are tested against two fundamental properties of clusters of galaxies: the cluster mass function and the cluster correlation function. We find that standard biased CDM models are inconsistent with these observations for any bias parameter b. A low-density, low-bias CDM-type model, with or without a cosmological constant, appears to be consistent with both the cluster mass function and the cluster correlations. The low-density model agrees well with the observed correlation function of the Abell, Automatic Plate Measuring Facility (APM), and Edinburgh-Durham cluster catalogs. The model is in excellent agreement with the observed dependence of the correlation strength on cluster mean separation, reproducing the measured universal dimensionless cluster correlation. The low-density model is also consistent with other large-scale structure observations, including the APM angular galaxy-correlations, and for lambda = 1-Omega with the COBE results of the microwave background radiation fluctuations.

Improved organic thin-film transistor performance using novel self-assembled monolayers

NASA Astrophysics Data System (ADS)

McDowell, M.; Hill, I. G.; McDermott, J. E.; Bernasek, S. L.; Schwartz, J.

2006-02-01

Pentacene-based organic thin-film transistors have been fabricated using a phosphonate-linked anthracene self-assembled monolayer as a buffer between the silicon dioxide gate dielectric and the active pentacene channel region. Vast improvements in the subthreshold slope and threshold voltage are observed compared to control devices fabricated without the buffer. Both observations are consistent with a greatly reduced density of charge trapping states at the semiconductor-dielectric interface effected by introduction of the self-assembled monolayer.

Directed self-assembly of proteins into discrete radial patterns

PubMed Central

Thakur, Garima; Prashanthi, Kovur; Thundat, Thomas

2013-01-01

Unlike physical patterning of materials at nanometer scale, manipulating soft matter such as biomolecules into patterns is still in its infancy. Self-assembled monolayer (SAM) with surface density gradient has the capability to drive biomolecules in specific directions to create hierarchical and discrete structures. Here, we report on a two-step process of self-assembly of the human serum albumin (HSA) protein into discrete ring structures based on density gradient of SAM. The methodology involves first creating a 2-dimensional (2D) polyethylene glycol (PEG) islands with responsive carboxyl functionalities. Incubation of proteins on such pre-patterned surfaces results in direct self-assembly of protein molecules around PEG islands. Immobilization and adsorption of protein on such structures over time evolve into the self-assembled patterns. PMID:23719678

The KP hierarchy with self-consistent sources: construction, Wronskian solutions and bilinear identities

NASA Astrophysics Data System (ADS)

Lin, Runliang; Liu, Xiaojun; Zeng, Yunbo

2014-10-01

In this paper, we will present some of our results on the soliton hierarchy with self-consistent sources (SHSCSs). The Kadomtsev-Petviashvili (KP) hierarchy will be used as an illustrative example to show the method to construct the SHSCSs. Some properties of the KP hierarchy with self-consistent sources will also be given, such as the dressing approach, the Wronskian solutions (including soliton solutions), its bilinear identities and the tau function.

Ultrahigh-density sub-10 nm nanowire array formation via surface-controlled phase separation.

PubMed

Tian, Yuan; Mukherjee, Pinaki; Jayaraman, Tanjore V; Xu, Zhanping; Yu, Yongsheng; Tan, Li; Sellmyer, David J; Shield, Jeffrey E

2014-08-13

We present simple, self-assembled, and robust fabrication of ultrahigh density cobalt nanowire arrays. The binary Co-Al and Co-Si systems phase-separate during physical vapor deposition, resulting in Co nanowire arrays with average diameter as small as 4.9 nm and nanowire density on the order of 10(16)/m(2). The nanowire diameters were controlled by moderating the surface diffusivity, which affected the lateral diffusion lengths. High resolution transmission electron microscopy reveals that the Co nanowires formed in the face-centered cubic structure. Elemental mapping showed that in both systems the nanowires consisted of Co with undetectable Al or Si and that the matrix consisted of Al with no distinguishable Co in the Co-Al system and a mixture of Si and Co in the Co-Si system. Magnetic measurements clearly indicate anisotropic behavior consistent with shape anisotropy. The dynamics of nanowire growth, simulated using an Ising model, is consistent with the experimental phase and geometry of the nanowires.

A proposed simulation method for directed self-assembly of nanographene

NASA Astrophysics Data System (ADS)

Geraets, J. A.; Baldwin, J. P. C.; Twarock, R.; Hancock, Y.

2017-09-01

A methodology for predictive kinetic self-assembly modeling of bottom-up chemical synthesis of nanographene is proposed. The method maintains physical transparency in using a novel array format to efficiently store molecule information and by using array operations to determine reaction possibilities. Within a minimal model approach, the parameter space for the bond activation energies (i.e. molecule functionalization) at fixed reaction temperature and initial molecule concentrations is explored. Directed self-assembly of nanographene from functionalized tetrabenzanthracene and benzene is studied with regions in the activation energy phase-space showing length-to-width ratio tunability. The degree of defects and reaction reproducibility in the simulations is also determined, with the rate of functionalized benzene addition providing additional control of the dimension and quality of the nanographene. Comparison of the reaction energetics to available density functional theory data suggests the synthesis may be experimentally tenable using aryl-halide cross-coupling and noble metal surface-assisted catalysis. With full access to the intermediate reaction network and with dynamic coupling to density functional theory-informed tight-binding simulation, the method is proposed as a computationally efficient means towards detailed simulation-driven design of new nanographene systems.

Doubly self-consistent field theory of grafted polymers under simple shear in steady state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suo, Tongchuan; Whitmore, Mark D., E-mail: mark-whitmore@umanitoba.ca

2014-03-21

We present a generalization of the numerical self-consistent mean-field theory of polymers to the case of grafted polymers under simple shear. The general theoretical framework is presented, and then applied to three different chain models: rods, Gaussian chains, and finitely extensible nonlinear elastic (FENE) chains. The approach is self-consistent at two levels. First, for any flow field, the polymer density profile and effective potential are calculated self-consistently in a manner similar to the usual self-consistent field theory of polymers, except that the calculation is inherently two-dimensional even for a laterally homogeneous system. Second, through the use of a modified Brinkmanmore » equation, the flow field and the polymer profile are made self-consistent with respect to each other. For all chain models, we find that reasonable levels of shear cause the chains to tilt, but it has very little effect on the overall thickness of the polymer layer, causing a small decrease for rods, and an increase of no more than a few percent for the Gaussian and FENE chains. Using the FENE model, we also probe the individual bond lengths, bond correlations, and bond angles along the chains, the effects of the shear on them, and the solvent and bonded stress profiles. We find that the approximations needed within the theory for the Brinkman equation affect the bonded stress, but none of the other quantities.« less

Structure-property relationships in cubic cuprous iodide: A novel view on stability, chemical bonding, and electronic properties

NASA Astrophysics Data System (ADS)

Pishtshev, A.; Karazhanov, S. Zh.

2017-02-01

Based on the combination of density functional theory and theory-group methods, we performed systematic modeling of γ-CuI structural design at the atomistic level. Being started from the metallic copper lattice, we treated a crystal assembly as a stepwise iodination process characterized in terms of a sequence of intermediate lattice geometries. These geometries were selected and validated via screening of possible structural transformations. The genesis of chemical bonding was studied for three structural transformations by analyzing the relevant changes in the topology of valence electron densities. We determined structural trends driven by metal-ligand coupling. This allowed us to suggest the improved scenario of chemical bonding in γ-CuI. In particular, the unconventional effect of spatial separation of metallic and covalent interactions was found to be very important with respect to the preferred arrangements of valence electrons in the iodination process. We rigorously showed that useful electronic and optical properties of γ-CuI originate from the combination of two separated bonding patterns—strong covalency established in I-Cu tetrahedral connections and noncovalent interactions of copper cores is caused by the 3d10 closed-shell electron configurations. The other finding of ours is that the self-consistency of the GW calculations is crucial for correctly determining the dynamic electronic correlations in γ-CuI. Detail reinvestigation of the quasi-particle energy structure by means of the self-consistent GW approach allowed us to explain how p-type electrical conductivity can be engineered in the material.

Martian Dust Devil Electron Avalanche Process and Associated Electrochemistry

NASA Technical Reports Server (NTRS)

Jackson, Telana L.; Farrell, William M.; Delory, Gregory T.; Nithianandam, Jeyasingh

2010-01-01

Mars' dynamic atmosphere displays localized dust devils and larger, global dust storms. Based on terrestrial analog studies, electrostatic modeling, and laboratory work these features will contain large electrostatic fields formed via triboelectric processes. In the low-pressure Martian atmosphere, these fields may create an electron avalanche and collisional plasma due to an increase in electron density driven by the internal electrical forces. To test the hypothesis that an electron avalanche is sustained under these conditions, a self-consistent atmospheric process model is created including electron impact ionization sources and electron losses via dust absorption, electron dissociation attachment, and electron/ion recombination. This new model is called the Dust Devil Electron Avalanche Model (DDEAM). This model solves simultaneously nine continuity equations describing the evolution of the primary gaseous chemical species involved in the electrochemistry. DDEAM monitors the evolution of the electrons and primary gas constituents, including electron/water interactions. We especially focus on electron dynamics and follow the electrons as they evolve in the E field driven collisional gas. When sources and losses are self-consistently included in the electron continuity equation, the electron density grows exponentially with increasing electric field, reaching an equilibrium that forms a sustained time-stable collisional plasma. However, the character of this plasma differs depending upon the assumed growth rate saturation process (chemical saturation versus space charge). DDEAM also shows the possibility of the loss of atmospheric methane as a function of electric field due to electron dissociative attachment of the hydrocarbon. The methane destruction rates are presented and can be included in other larger atmospheric models.

REVIEW ARTICLE: On correlation effects in electron spectroscopies and the GW approximation

NASA Astrophysics Data System (ADS)

Hedin, Lars

1999-10-01

The GW approximation (GWA) extends the well-known Hartree-Fock approximation (HFA) for the self-energy (exchange potential), by replacing the bare Coulomb potential v by the dynamically screened potential W, e.g. Vex = iGv is replaced by icons/Journals/Common/Sigma" ALT="Sigma" ALIGN="TOP"/>GW = iGW. Here G is the one-electron Green's function. The GWA like the HFA is self-consistent, which allows for solutions beyond perturbation theory, like say spin-density waves. In a first approximation, iGW is a sum of a statically screened exchange potential plus a Coulomb hole (equal to the electrostatic energy associated with the charge pushed away around a given electron). The Coulomb hole part is larger in magnitude, but the two parts give comparable contributions to the dispersion of the quasi-particle energy. The GWA can be said to describe an electronic polaron (an electron surrounded by an electronic polarization cloud), which has great similarities to the ordinary polaron (an electron surrounded by a cloud of phonons). The dynamical screening adds new crucial features beyond the HFA. With the GWA not only bandstructures but also spectral functions can be calculated, as well as charge densities, momentum distributions, and total energies. We will discuss the ideas behind the GWA, and generalizations which are necessary to improve on the rather poor GWA satellite structures in the spectral functions. We will further extend the GWA approach to fully describe spectroscopies like photoemission, x-ray absorption, and electron scattering. Finally we will comment on the relation between the GWA and theories for strongly correlated electronic systems. In collecting the material for this review, a number of new results and perspectives became apparent, which have not been published elsewhere.

Prevalence and functions of non-suicidal self-injury in Spanish adolescents.

PubMed

Calvete, Esther; Orue, Izaskun; Aizpuru, Leire; Brotherton, Hardin

2015-01-01

This study examined the prevalence, characteristics and functions of Non-suicidal Self-injury (NSSI) among Spanish adolescents. The sample consisted of 1,864 adolescents aged between 12 and 19 years (Mean Age = 15.32, SD = 1.97, 51.45% girls). The participants completed a modified version of the self-report scale Functional Assessment of Self-Mutilation (FASM; Lloyd, Kelley, & Hope, 1997) to assess rates and methods of NSSI used during the last 12 months. They also indicated the functions of NSSI. NSSI behaviors are common among Spanish adolescents. More than half of the sample showed such behavior in the past year, and 32.2% had carried out severe NSSI behaviors. The functions of NSSI were examined by using confirmatory factor analyses. Results supported a hierarchical model consisting of two second-order factors: automatic reinforcement, which explained both positive and negative automatic reinforcement, and social reinforcement, which explained both positive and negative social reinforcement. These dimensions are critical to understand the factors that maintain NSSI behavior and have implications for treatments.

Maintenance cost, toppling risk and size of trees in a self-thinning stand.

PubMed

Larjavaara, Markku

2010-07-07

Wind routinely topples trees during storms, and the likelihood that a tree is toppled depends critically on its allometry. Yet none of the existing theories to explain tree allometry consider wind drag on tree canopies. Since leaf area index in crowded, self-thinning stands is independent of stand density, the drag force per unit land can also be assumed to be independent of stand density, with only canopy height influencing the total toppling moment. Tree stem dimensions and the self-thinning biomass can then be computed by further assuming that the risk of toppling over and stem maintenance per unit land area are independent of stand density, and that stem maintenance cost is a linear function of stem surface area and sapwood volume. These assumptions provide a novel way to understand tree allometry and lead to a self-thinning line relating tree biomass and stand density with a power between -3/2 and -2/3 depending on the ratio of maintenance of sapwood and stem surface. (c) 2010 Elsevier Ltd. All rights reserved.

K- and L-edge X-ray absorption spectrum calculations of closed-shell carbon, silicon, germanium, and sulfur compounds using damped four-component density functional response theory.

PubMed

Fransson, Thomas; Burdakova, Daria; Norman, Patrick

2016-05-21

X-ray absorption spectra of carbon, silicon, germanium, and sulfur compounds have been investigated by means of damped four-component density functional response theory. It is demonstrated that a reliable description of relativistic effects is obtained at both K- and L-edges. Notably, an excellent agreement with experimental results is obtained for L2,3-spectra-with spin-orbit effects well accounted for-also in cases when the experimental intensity ratio deviates from the statistical one of 2 : 1. The theoretical results are consistent with calculations using standard response theory as well as recently reported real-time propagation methods in time-dependent density functional theory, and the virtues of different approaches are discussed. As compared to silane and silicon tetrachloride, an anomalous error in the absolute energy is reported for the L2,3-spectrum of silicon tetrafluoride, amounting to an additional spectral shift of ∼1 eV. This anomaly is also observed for other exchange-correlation functionals, but it is seen neither at other silicon edges nor at the carbon K-edge of fluorine derivatives of ethene. Considering the series of molecules SiH4-XFX with X = 1, 2, 3, 4, a gradual divergence from interpolated experimental ionization potentials is observed at the level of Kohn-Sham density functional theory (DFT), and to a smaller extent with the use of Hartree-Fock. This anomalous error is thus attributed partly to difficulties in correctly emulating the electronic structure effects imposed by the very electronegative fluorines, and partly due to inconsistencies in the spurious electron self-repulsion in DFT. Substitution with one, or possibly two, fluorine atoms is estimated to yield small enough errors to allow for reliable interpretations and predictions of L2,3-spectra of more complex and extended silicon-based systems.

Properties of a planar electric double layer under extreme conditions investigated by classical density functional theory and Monte Carlo simulations.

PubMed

Zhou, Shiqi; Lamperski, Stanisław; Zydorczak, Maria

2014-08-14

Monte Carlo (MC) simulation and classical density functional theory (DFT) results are reported for the structural and electrostatic properties of a planar electric double layer containing ions having highly asymmetric diameters or valencies under extreme concentration condition. In the applied DFT, for the excess free energy contribution due to the hard sphere repulsion, a recently elaborated extended form of the fundamental measure functional is used, and coupling of Coulombic and short range hard-sphere repulsion is described by a traditional second-order functional perturbation expansion approximation. Comparison between the MC and DFT results indicates that validity interval of the traditional DFT approximation expands to high ion valences running up to 3 and size asymmetry high up to diameter ratio of 4 whether the high valence ions or the large size ion are co- or counter-ions; and to a high bulk electrolyte concentration being close to the upper limit of the electrolyte mole concentration the MC simulation can deal with well. The DFT accuracy dependence on the ion parameters can be self-consistently explained using arguments of liquid state theory, and new EDL phenomena such as overscreening effect due to monovalent counter-ions, extreme layering effect of counter-ions, and appearance of a depletion layer with almost no counter- and co-ions are observed.

Industrial entrepreneurial network: Structural and functional analysis

NASA Astrophysics Data System (ADS)

Medvedeva, M. A.; Davletbaev, R. H.; Berg, D. B.; Nazarova, J. J.; Parusheva, S. S.

2016-12-01

Structure and functioning of two model industrial entrepreneurial networks are investigated in the present paper. One of these networks is forming when implementing an integrated project and consists of eight agents, which interact with each other and external environment. The other one is obtained from the municipal economy and is based on the set of the 12 real business entities. Analysis of the networks is carried out on the basis of the matrix of mutual payments aggregated over the certain time period. The matrix is created by the methods of experimental economics. Social Network Analysis (SNA) methods and instruments were used in the present research. The set of basic structural characteristics was investigated: set of quantitative parameters such as density, diameter, clustering coefficient, different kinds of centrality, and etc. They were compared with the random Bernoulli graphs of the corresponding size and density. Discovered variations of random and entrepreneurial networks structure are explained by the peculiarities of agents functioning in production network. Separately, were identified the closed exchange circuits (cyclically closed contours of graph) forming an autopoietic (self-replicating) network pattern. The purpose of the functional analysis was to identify the contribution of the autopoietic network pattern in its gross product. It was found that the magnitude of this contribution is more than 20%. Such value allows using of the complementary currency in order to stimulate economic activity of network agents.

Theoretical modeling of electronic transport in molecular devices

NASA Astrophysics Data System (ADS)

Piccinin, Simone

In this thesis a novel approach for simulating electronic transport in nanoscale structures is introduced. We consider an open quantum system (the electrons of structure) accelerated by an external electromotive force and dissipating energy through inelastic scattering with a heat bath (phonons) acting on the electrons. This method can be regarded as a quantum-mechanical extension of the semi-classical Boltzmann transport equation. We use periodic boundary conditions and employ Density Functional Theory to recast the many-particle problem in an effective single-particle mean-field problem. By explicitly treating the dissipation in the electrodes, the behavior of the potential is an outcome of our method, at variance with the scattering approaches based on the Landauer formalism. We study the self-consistent steady-state solution, analyzing the out-of-equilibrium electron distribution, the electrical characteristics, the behavior of the self-consistent potential and the density of states of the system. We apply the method to the study of electronic transport in several molecular devices, consisting of small organic molecules or atomic wires sandwiched between gold surfaces. For gold wires we recover the experimental evidence that transport in short wires is ballistic, independent of the length of the wire and with conductance of one quantum. In benzene-1,4-dithiol we find that the delocalization of the frontier orbitals of the molecule is responsible for the high value of conductance and that, by inserting methylene groups to decouple the sulfur atoms from the carbon ring, the current is reduced, in agreement with the experimental measurements. We study the effect a geometrical distortion in a molecular device, namely the relative rotation of the carbon rings in a biphenyl-4,4'-dithiol molecule. We find that the reduced coupling between pi orbitals of the rings induced by the rotation leads to a reduction of the conductance and that this behavior is captured by a simple two level model. Finally the transport properties of alkanethiol monolayers are analyzed by means of the local density of states at the Fermi energy: we find an exponential dependence of the current on the length of the chain, in quantitative agreement with the corresponding experiments.

Energy level alignment of self-assembled linear chains of benzenediamine on Au(111) from first principles

NASA Astrophysics Data System (ADS)

Li, Guo; Rangel, Tonatiuh; Liu, Zhen-Fei; Cooper, Valentino R.; Neaton, Jeffrey B.

2016-03-01

Using density functional theory (DFT) with a van der Waals density functional, we calculate the adsorption energetics and geometry of benzenediamine (BDA) molecules on Au(111) surfaces. Our results demonstrate that the reported self-assembled linear chain structure of BDA, stabilized via hydrogen bonds between amine groups, is energetically favored over previously studied monomeric phases. Moreover, using a model, which includes nonlocal polarization effects from the substrate and the neighboring molecules and incorporates many-body perturbation theory calculations within the GW approximation, we obtain approximate self-energy corrections to the DFT highest occupied molecular orbital (HOMO) energy associated with BDA adsorbate phases. We find that, independent of coverage, the HOMO energy of the linear chain phase is lower relative to the Fermi energy than that of the monomer phase, and in good agreement with values measured with ultraviolet photoelectron spectroscopy and x-ray photoelectron spectroscopy.

Collective ratchet effects and reversals for active matter particles on quasi-one-dimensional asymmetric substrates.

PubMed

McDermott, Danielle; Olson Reichhardt, Cynthia J; Reichhardt, Charles

2016-10-19

Using computer simulations, we study a two-dimensional system of sterically interacting self-mobile run-and-tumble disk-shaped particles with an underlying periodic quasi-one-dimensional asymmetric substrate, and show that a rich variety of collective active ratchet behaviors arise as a function of particle density, activity, substrate period, and the maximum force exerted by the substrate. The net dc drift, or ratchet transport flux, is nonmonotonic since it increases with increased activity but is diminished by the onset of self-clustering of the active particles. Increasing the particle density decreases the ratchet transport flux for shallow substrates but increases the ratchet transport flux for deep substrates due to collective hopping events. At the highest particle densities, the ratchet motion is destroyed by a self-jamming effect. We show that it is possible to realize reversals of the direction of the net dc drift in the deep substrate limit when multiple rows of active particles can be confined in each substrate minimum, permitting emergent particle-like excitations to appear that experience an inverted effective substrate potential. We map out a phase diagram of the forward and reverse ratchet effects as a function of the particle density, activity, and substrate properties.

Predictors of Positive Outcomes in Offspring of Depressed Parents and Non-depressed Parents Across 20 Years

PubMed Central

Verdeli, Helen; Wickramaratne, Priya; Warner, Virginia; Mancini, Anthony; Weissman, Myrna

2014-01-01

Understanding differences in factors leading to positive outcomes in high-risk and low-risk offspring has important implications for preventive interventions. We identified variables predicting positive outcomes in a cohort of 235 offspring from 76 families in which one, both, or neither parent had major depressive disorder. Positive outcomes were termed resilient in offspring of depressed parents, and competent in offspring of non-depressed parents, and defined by two separate criteria: absence of psychiatric diagnosis and consistently high functioning at 2, 10, and 20 years follow-up. In offspring of depressed parents, easier temperament and higher self-esteem were associated with greater odds of resilient outcome defined by absence of diagnosis. Lower maternal overprotection, greater offspring self-esteem, and higher IQ were associated with greater odds of resilient outcome defined by consistently high functioning. Multivariate analysis indicated that resilient outcome defined by absence of diagnosis was best predicted by offspring self-esteem; resilient outcome defined by functioning was best predicted by maternal overprotection and self-esteem. Among offspring of non-depressed parents, greater family cohesion, easier temperament and higher self-esteem were associated with greater odds of offspring competent outcome defined by absence of diagnosis. Higher maternal affection and greater offspring self-esteem were associated with greater odds of competent outcome, defined by consistently high functioning. Multivariate analysis for each criterion indicated that competent outcome was best predicted by offspring self-esteem. As the most robust predictor of positive outcomes in offspring of depressed and non-depressed parents, self-esteem is an important target for youth preventive interventions. PMID:25374449

A new model for gravitational potential perturbations in disks of spiral galaxies. An application to our Galaxy

NASA Astrophysics Data System (ADS)

Junqueira, T. C.; Lépine, J. R. D.; Braga, C. A. S.; Barros, D. A.

2013-02-01

Aims: We propose a new, more realistic description of the perturbed gravitational potential of spiral galaxies, with spiral arms having Gaussian-shaped groove profiles. The aim is to reach a self-consistent description of the spiral structure, that is, one in which an initial potential perturbation generates, by means of the stellar orbits, spiral arms with a profile similar to that of the imposed perturbation. Self-consistency is a condition for having long-lived structures. Methods: Using the new perturbed potential, we investigate the stable stellar orbits in galactic disks for galaxies with no bar or with only a weak bar. The model is applied to our Galaxy by making use of the axisymmetric component of the potential computed from the Galactic rotation curve, in addition to other input parameters similar to those of our Galaxy. The influence of the bulge mass on the stellar orbits in the inner regions of a disk is also investigated. Results: The new description offers the advantage of easy control of the parameters of the Gaussian profile of its potential. We compute the density contrast between arm and inter-arm regions. We find a range of values for the perturbation amplitude from 400 to 800 km2 s-2 kpc-1, which implies an approximate maximum ratio of the tangential force to the axisymmetric force between 3% and 6%. Good self-consistency of arm shapes is obtained between the Inner Lindblad resonance (ILR) and the 4:1 resonance. Near the 4:1 resonance the response density starts to deviate from the imposed logarithmic spiral form. This creates bifurcations that appear as short arms. Therefore the deviation from a perfect logarithmic spiral in galaxies can be understood as a natural effect of the 4:1 resonance. Beyond the 4:1 resonance we find closed orbits that have similarities with the arms observed in our Galaxy. In regions near the center, elongated stellar orbits appear naturally, in the presence of a massive bulge, without imposing any bar-shaped potential, but only extending the spiral perturbation a little inward of the ILR. This suggests that a bar is formed with a half-size ~3 kpc by a mechanism similar to that of the spiral arms. Conclusions: The potential energy perturbation that we adopted represents an important step in the direction of self-consistency, compared to previous sine function descriptions of the potential. In addition, our model produces a realistic description of the spiral structure, which is able to explain several details that were not yet understood.

Star cluster formation in a turbulent molecular cloud self-regulated by photoionization feedback

NASA Astrophysics Data System (ADS)

Gavagnin, Elena; Bleuler, Andreas; Rosdahl, Joakim; Teyssier, Romain

2017-12-01

Most stars in the Galaxy are believed to be formed within star clusters from collapsing molecular clouds. However, the complete process of star formation, from the parent cloud to a gas-free star cluster, is still poorly understood. We perform radiation-hydrodynamical simulations of the collapse of a turbulent molecular cloud using the RAMSES-RT code. Stars are modelled using sink particles, from which we self-consistently follow the propagation of the ionizing radiation. We study how different feedback models affect the gas expulsion from the cloud and how they shape the final properties of the emerging star cluster. We find that the star formation efficiency is lower for stronger feedback models. Feedback also changes the high-mass end of the stellar mass function. Stronger feedback also allows the establishment of a lower density star cluster, which can maintain a virial or sub-virial state. In the absence of feedback, the star formation efficiency is very high, as well as the final stellar density. As a result, high-energy close encounters make the cluster evaporate quickly. Other indicators, such as mass segregation, statistics of multiple systems and escaping stars confirm this picture. Observations of young star clusters are in best agreement with our strong feedback simulation.

Transport across nanogaps using self-consistent boundary conditions

NASA Astrophysics Data System (ADS)

Biswas, D.; Kumar, R.

2012-06-01

Charge particle transport across nanogaps is studied theoretically within the Schrodinger-Poisson mean field framework. The determination of self-consistent boundary conditions across the gap forms the central theme in order to allow for realistic interface potentials (such as metal-vacuum) which are smooth at the boundary and do not abruptly assume a constant value at the interface. It is shown that a semiclassical expansion of the transmitted wavefunction leads to approximate but self consistent boundary conditions without assuming any specific form of the potential beyond the gap. Neglecting the exchange and correlation potentials, the quantum Child-Langmuir law is investigated. It is shown that at zero injection energy, the quantum limiting current density (Jc) is found to obey the local scaling law Jc ~ Vgα/D5-2α with the gap separation D and voltage Vg. The exponent α > 1.1 with α → 3/2 in the classical regime of small de Broglie wavelengths.

Electronic structure and charge transfer excited states of endohedral fullerene containing electron donoracceptor complexes utilized in organic photovoltaics

NASA Astrophysics Data System (ADS)

Amerikheirabadi, Fatemeh

Organic Donor-Acceptor complexes form the main component of the organic photovoltaic devices (OPVs). The open circuit voltage of OPVs is directly related to the charge transfer excited state energies of these complexes. Currently a large number of different molecular complexes are being tested for their efficiency in photovoltaic devices. In this work, density functional theory as implemented in the NRLMOL code is used to investigate the electronic structure and related properties of these donor-acceptor complexes. The charge transfer excitation energies are calculated using the perturbative delta self-consistent field method recently developed in our group as the standard time dependent density functional approaches fail to accurately provide them. The model photovoltaics systems analyzed are as follows: Sc3N C 80--ZnTPP, Y3 N C80-- ZnTPP and Sc3 N C80-- ZnPc. In addition, a thorough analysis of the isolated donor and acceptor molecules is also provided. The studied acceptors are chosen from a class of fullerenes named trimetallic nitride endohedral fullerenes. These molecules have shown to possess advantages as acceptors such as long lifetimes of the charge-separated states.

Strong correlation effects in theoretical STM studies of magnetic adatoms

NASA Astrophysics Data System (ADS)

Dang, Hung T.; dos Santos Dias, Manuel; Liebsch, Ansgar; Lounis, Samir

2016-03-01

We present a theoretical study for the scanning tunneling microscopy (STM) spectra of surface-supported magnetic nanostructures, incorporating strong correlation effects. As concrete examples, we study Co and Mn adatoms on the Cu(111) surface, which are expected to represent the opposite limits of Kondo physics and local moment behavior, using a combination of density functional theory and both quantum Monte Carlo and exact diagonalization impurity solvers. We examine in detail the effects of temperature T , correlation strength U , and impurity d electron occupancy Nd on the local density of states. We also study the effective coherence energy scale, i.e., the Kondo temperature TK, which can be extracted from the STM spectra. Theoretical STM spectra are computed as a function of STM tip position relative to each adatom. Because of the multiorbital nature of the adatoms, the STM spectra are shown to consist of a complicated superposition of orbital contributions, with different orbital symmetries, self-energies, and Kondo temperatures. For a Mn adatom, which is close to half-filling, the STM spectra are featureless near the Fermi level. On the other hand, the quasiparticle peak for a Co adatom gives rise to strongly position-dependent Fano line shapes.

Low-energy isovector and isoscalar dipole response in neutron-rich nuclei

NASA Astrophysics Data System (ADS)

Vretenar, D.; Niu, Y. F.; Paar, N.; Meng, J.

2012-04-01

The self-consistent random-phase approximation, based on the framework of relativistic energy density functionals, is employed in the study of isovector and isoscalar dipole response in 68Ni,132Sn, and 208Pb. The evolution of pygmy dipole states (PDSs) in the region of low excitation energies is analyzed as a function of the density dependence of the symmetry energy for a set of relativistic effective interactions. The occurrence of PDSs is predicted in the response to both the isovector and the isoscalar dipole operators, and its strength is enhanced with the increase in the symmetry energy at saturation and the slope of the symmetry energy. In both channels, the PDS exhausts a relatively small fraction of the energy-weighted sum rule but a much larger percentage of the inverse energy-weighted sum rule. For the isovector dipole operator, the reduced transition probability B(E1) of the PDSs is generally small because of pronounced cancellation of neutron and proton partial contributions. The isoscalar-reduced transition amplitude is predominantly determined by neutron particle-hole configurations, most of which add coherently, and this results in a collective response of the PDSs to the isoscalar dipole operator.

Combined ab initio and density functional study on polaron to bipolaron transitions in oligophenyls and oligothiophenes

NASA Astrophysics Data System (ADS)

Irle, Stephan; Lischka, Hans

1997-08-01

Ab initio self-consistent-field (SCF), two-configuration SCF (TCSCF), and density functional theory (DFT) calculations on the charge-transfer complexes of doubly Li/Cl-doped oligothiophenes and oligo(p-phenyls) and on respective charged systems without counterions have been carried out in order to study polaron to bipolaron transitions. Oligomer chains up to octamers and the ring structures cyclo-dodecathiophene and cyclo-dodeca(p-phenyl) have been investigated. Special attention is paid to the open-shell biradical character of two isolated polaronic defects. It is found that the TCSCF and the spin-unrestricted DFT methods can be successfully applied. A bipolaron structure is obtained when the doping atoms are located on neighboring rings and when there is one undoped ring separating the two doped ones. If there are two or more undoped rings in between a two-polaron configuration (biradical) is found. The bipolaron system is calculated to be more stable than the two-polaron case when counterions are taken into account. The stabilities are reversed if the bare, doubly-charged systems are considered. A theoretical estimate for the barrier height of the polaron to bipolaron transition is given using model reaction coordinates.

Communication: Two-step explosion processes of highly charged fullerene cations C{sub 60}{sup q+} (q = 20–60)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamazaki, Kaoru; Nakamura, Takashi; Kanno, Manabu

2014-09-28

To establish the fundamental understanding of the fragmentation dynamics of highly positive charged nano- and bio-materials, we carried out on-the-fly classical trajectory calculations on the fragmentation dynamics of C{sub 60}{sup q+} (q = 20–60). We used the UB3LYP/3-21G level of density functional theory and the self-consistent charge density-functional based tight-binding theory. For q ≥ 20, we found that a two-step explosion mechanism governs the fragmentation dynamics: C{sub 60}{sup q+} first ejects singly and multiply charged fast atomic cations C{sup z+} (z ≥ 1) via Coulomb explosions on a timescale of 10 fs to stabilize the remaining core cluster. Thermal evaporationsmore » of slow atomic and molecular fragments from the core cluster subsequently occur on a timescale of 100 fs to 1 ps. Increasing the charge q makes the fragments smaller. This two-step mechanism governs the fragmentation dynamics in the most likely case that the initial kinetic energy accumulated upon ionization to C{sub 60}{sup q+} by ion impact or X-ray free electron laser is larger than 100 eV.« less

Effect of exponential density transition on self-focusing of q-Gaussian laser beam in collisionless plasma

NASA Astrophysics Data System (ADS)

Valkunde, Amol T.; Vhanmore, Bandopant D.; Urunkar, Trupti U.; Gavade, Kusum M.; Patil, Sandip D.; Takale, Mansing V.

2018-05-01

In this work, nonlinear aspects of a high intensity q-Gaussian laser beam propagating in collisionless plasma having upward density ramp of exponential profiles is studied. We have employed the nonlinearity in dielectric function of plasma by considering ponderomotive nonlinearity. The differential equation governing the dimensionless beam width parameter is achieved by using Wentzel-Kramers-Brillouin (WKB) and paraxial approximations and solved it numerically by using Runge-Kutta fourth order method. Effect of exponential density ramp profile on self-focusing of q-Gaussian laser beam for various values of q is systematically carried out and compared with results Gaussian laser beam propagating in collisionless plasma having uniform density. It is found that exponential plasma density ramp causes the laser beam to become more focused and gives reasonably interesting results.

Non-Born-Oppenheimer self-consistent field calculations with cubic scaling

NASA Astrophysics Data System (ADS)

Moncada, Félix; Posada, Edwin; Flores-Moreno, Roberto; Reyes, Andrés

2012-05-01

An efficient nuclear molecular orbital methodology is presented. This approach combines an auxiliary density functional theory for electrons (ADFT) and a localized Hartree product (LHP) representation for the nuclear wave function. A series of test calculations conducted on small molecules exposed that energy and geometry errors introduced by the use of ADFT and LHP approximations are small and comparable to those obtained by the use of electronic ADFT. In addition, sample calculations performed on (HF)n chains disclosed that the combined ADFT/LHP approach scales cubically with system size (n) as opposed to the quartic scaling of Hartree-Fock/LHP or DFT/LHP methods. Even for medium size molecules the improved scaling of the ADFT/LHP approach resulted in speedups of at least 5x with respect to Hartree-Fock/LHP calculations. The ADFT/LHP method opens up the possibility of studying nuclear quantum effects on large size systems that otherwise would be impractical.

Fission properties of superheavy nuclei for r -process calculations

NASA Astrophysics Data System (ADS)

Giuliani, Samuel A.; Martínez-Pinedo, Gabriel; Robledo, Luis M.

2018-03-01

We computed a new set of static fission properties suited for r -process calculations. The potential energy surfaces and collective inertias of 3640 nuclei in the superheavy region are obtained from self-consistent mean-field calculations using the Barcelona-Catania-Paris-Madrid energy density functional. The fission path is computed as a function of the quadrupole moment by minimizing the potential energy and exploring octupole and hexadecapole deformations. The spontaneous fission lifetimes are evaluated employing different schemes for the collective inertias and vibrational energy corrections. This allows us to explore the sensitivity of the lifetimes to those quantities together with the collective ground-state energy along the superheavy landscape. We computed neutron-induced stellar reaction rates relevant for r -process nucleosynthesis using the Hauser-Feshbach statistical approach and study the impact of collective inertias. The competition between different reaction channels including neutron-induced rates, spontaneous fission, and α decay is discussed for typical r -process conditions.

Semiclassical magnetotransport in strongly spin-orbit coupled Rashba two-dimensional electron systems.

PubMed

Xiao, Cong; Li, Dingping

2016-06-15

Semiclassical magnetoelectric and magnetothermoelectric transport in strongly spin-orbit coupled Rashba two-dimensional electron systems is investigated. In the presence of a perpendicular classically weak magnetic field and short-range impurity scattering, we solve the linearized Boltzmann equation self-consistently. Using the solution, it is found that when Fermi energy E F locates below the band crossing point (BCP), the Hall coefficient is a nonmonotonic function of electron density n e and not inversely proportional to n e. While the magnetoresistance (MR) and Nernst coefficient vanish when E F locates above the BCP, non-zero MR and enhanced Nernst coefficient emerge when E F decreases below the BCP. Both of them are nonmonotonic functions of E F below the BCP. The different semiclassical magnetotransport behaviors between the two sides of the BCP can be helpful to experimental identifications of the band valley regime and topological change of Fermi surface in considered systems.

Semiclassical magnetotransport in strongly spin-orbit coupled Rashba two-dimensional electron systems

NASA Astrophysics Data System (ADS)

Xiao, Cong; Li, Dingping

2016-06-01

Semiclassical magnetoelectric and magnetothermoelectric transport in strongly spin-orbit coupled Rashba two-dimensional electron systems is investigated. In the presence of a perpendicular classically weak magnetic field and short-range impurity scattering, we solve the linearized Boltzmann equation self-consistently. Using the solution, it is found that when Fermi energy E F locates below the band crossing point (BCP), the Hall coefficient is a nonmonotonic function of electron density n e and not inversely proportional to n e. While the magnetoresistance (MR) and Nernst coefficient vanish when E F locates above the BCP, non-zero MR and enhanced Nernst coefficient emerge when E F decreases below the BCP. Both of them are nonmonotonic functions of E F below the BCP. The different semiclassical magnetotransport behaviors between the two sides of the BCP can be helpful to experimental identifications of the band valley regime and topological change of Fermi surface in considered systems.

Reprint of "Theoretical description of metal/oxide interfacial properties: The case of MgO/Ag(001)"

NASA Astrophysics Data System (ADS)

Prada, Stefano; Giordano, Livia; Pacchioni, Gianfranco; Goniakowski, Jacek

2017-02-01

We compare the performances of different DFT functionals applied to ultra-thin MgO(100) films supported on the Ag(100) surface, a prototypical system of a weakly interacting oxide/metal interface, extensively studied in the past. Beyond semi-local DFT-GGA approximation, we also use the hybrid DFT-HSE approach to improve the description of the oxide electronic structure. Moreover, to better account for the interfacial adhesion, we include the van de Waals interactions by means of either the semi-empirical force fields by Grimme (DFT-D2 and DFT-D2*) or the self-consistent density functional optB88-vdW. We compare and discuss the results on the structural, electronic, and adhesion characteristics of the interface as obtained for pristine and oxygen-deficient Ag-supported MgO films in the 1-4 ML thickness range.

Theoretical description of metal/oxide interfacial properties: The case of MgO/Ag(001)

NASA Astrophysics Data System (ADS)

Prada, Stefano; Giordano, Livia; Pacchioni, Gianfranco; Goniakowski, Jacek

2016-12-01

We compare the performances of different DFT functionals applied to ultra-thin MgO(100) films supported on the Ag(100) surface, a prototypical system of a weakly interacting oxide/metal interface, extensively studied in the past. Beyond semi-local DFT-GGA approximation, we also use the hybrid DFT-HSE approach to improve the description of the oxide electronic structure. Moreover, to better account for the interfacial adhesion, we include the van de Waals interactions by means of either the semi-empirical force fields by Grimme (DFT-D2 and DFT-D2*) or the self-consistent density functional optB88-vdW. We compare and discuss the results on the structural, electronic, and adhesion characteristics of the interface as obtained for pristine and oxygen-deficient Ag-supported MgO films in the 1-4 ML thickness range.

Does self-efficacy influence recovery and well-being in osteoarthritis patients undergoing joint replacement? A systematic review.

PubMed

Magklara, Eleni; Burton, Christopher R; Morrison, Val

2014-09-01

To investigate the role of self-efficacy in functional recovery and well-being outcomes in osteoarthritis patients, undergoing hip or knee replacement surgery. Studies were identified using MEDLINE via PUB med, PsycINFO and CINAHL from inception to July 2013. Three search strategies that combined key terms of 'self-efficacy', 'functional recovery', 'well-being' and 'joint replacement' were applied. Titles and abstracts were screened for eligibility and, accordingly, potentially eligible studies were retrieved for review. Included studies were assessed in terms of their quality, and data were extracted by two independent reviewers. A narrative synthesis of results was conducted. In total, 836 articles were identified and after electronic de-duplication, 708 articles remained. After screening 15 articles were retrieved as potentially eligible and eight articles were included in the review. Of the eight studies (n = 967 patients), seven had a prospective design and all studies were considered of good quality. No fully conclusive evidence for the influence of self-efficacy upon functional recovery outcomes was found. When the timing of self-efficacy measurement was examined, post-operative self-efficacy was found to be related to functional recovery outcomes. Presurgical self-efficacy was the least consistent predictor of functional outcomes while postoperative self-efficacy was more consistently associated with recovery outcomes such as longer distance ambulation, exercise repetition and frequency, walking speed and disability. © The Author(s) 2014.

Self-Consistent Model of Magnetospheric Ring Current and Electromagnetic Ion Cyclotron Waves: The 2-7 May 1998 Storm

NASA Technical Reports Server (NTRS)

Khazanov, G. V.; Gamayunov, K. V.; Jordanova, V. K.

2003-01-01

A complete description of a self-consistent model of magnetospheric ring current interacting with electromagnetic ion cyclotron waves is presented. The model is based on the system of two kinetic equations; one equation describes the ring current ion dynamics, and another equation describes the wave evolution. The effects on ring current ions interacting with electromagnetic ion cyclotron waves and back on waves are considered self-consistently by solving both equations on a global magnetospheric scale under nonsteady state conditions. The developed model is employed to simulate the entire 2-7 May 1998 storm period. First, the trapped number fluxes of the ring current protons are calculated and presented along with comparison with the data measured by the three- dimensional hot plasma instrument Polar/HYDRA. Incorporating in the model the wave-particle interaction leads to much better agreement between the experimental data and the model results. Second, examining of the wave (MLT, L shell) distributions produced by the model during the storm progress reveals an essential intensification of the wave emission about 2 days after the main phase of the storm. This result is well consistent with the earlier ground-based observations. Finally, the theoretical shapes and the occurrence rates of the wave power spectral densities are studied. It is found that about 2 days after the storm s main phase on 4 May, mainly non-Gaussian shapes of power spectral densities are produced.

Electronic and optical properties of titanium nitride bulk and surfaces from first principles calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mehmood, Faisal; General Dynamics Information Technology, Inc., Dayton, Ohio 45433; Pachter, Ruth, E-mail: ruth.pachter@us.af.mil

Prediction of the frequency-dependent dielectric function of thin films poses computational challenges, and at the same time experimental characterization by spectroscopic ellipsometry remains difficult to interpret because of changes in stoichiometry and surface morphology, temperature, thickness of the film, or substrate. In this work, we report calculations for titanium nitride (TiN), a promising material for plasmonic applications because of less loss and other practical advantages compared to noble metals. We investigated structural, electronic, and optical properties of stoichiometric bulk TiN, as well as of the TiN(100), TiN(110), and TiN(111) outermost surfaces. Density functional theory (DFT) and many-body GW methods (Green'smore » (G) function-based approximation with screened Coulomb interaction (W)) were used, ranging from G{sub 0}W{sub 0}, GW{sub 0} to partially self-consistent sc-GW{sub 0}, as well as the GW-BSE (Bethe-Salpeter equation) and time-dependent DFT (TDDFT) methods for prediction of the optical properties. Structural parameters and the band structure for bulk TiN were shown to be consistent with previous work. Calculated dielectric functions, plasma frequencies, reflectivity, and the electron energy loss spectrum demonstrated consistency with experiment at the GW{sub 0}-BSE level. Deviations from experimental data are expected due to varying experimental conditions. Comparison of our results to spectroscopic ellipsometry data for realistic nanostructures has shown that although TDDFT may provide a computationally feasible level of theory in evaluation of the dielectric function, application is subject to validation with GW-BSE calculations.« less

Charge dynamics of the antiferromagnetically ordered Mott insulator

NASA Astrophysics Data System (ADS)

Han, Xing-Jie; Liu, Yu; Liu, Zhi-Yuan; Li, Xin; Chen, Jing; Liao, Hai-Jun; Xie, Zhi-Yuan; Normand, B.; Xiang, Tao

2016-10-01

We introduce a slave-fermion formulation in which to study the charge dynamics of the half-filled Hubbard model on the square lattice. In this description, the charge degrees of freedom are represented by fermionic holons and doublons and the Mott-insulating characteristics of the ground state are the consequence of holon-doublon bound-state formation. The bosonic spin degrees of freedom are described by the antiferromagnetic Heisenberg model, yielding long-ranged (Néel) magnetic order at zero temperature. Within this framework and in the self-consistent Born approximation, we perform systematic calculations of the average double occupancy, the electronic density of states, the spectral function and the optical conductivity. Qualitatively, our method reproduces the lower and upper Hubbard bands, the spectral-weight transfer into a coherent quasiparticle band at their lower edges and the renormalisation of the Mott gap, which is associated with holon-doublon binding, due to the interactions of both quasiparticle species with the magnons. The zeros of the Green function at the chemical potential give the Luttinger volume, the poles of the self-energy reflect the underlying quasiparticle dispersion with a spin-renormalised hopping parameter and the optical gap is directly related to the Mott gap. Quantitatively, the square-lattice Hubbard model is one of the best-characterised problems in correlated condensed matter and many numerical calculations, all with different strengths and weaknesses, exist with which to benchmark our approach. From the semi-quantitative accuracy of our results for all but the weakest interaction strengths, we conclude that a self-consistent treatment of the spin-fluctuation effects on the charge degrees of freedom captures all the essential physics of the antiferromagnetic Mott-Hubbard insulator. We remark in addition that an analytical approximation with these properties serves a vital function in developing a full understanding of the fundamental physics of the Mott state, both in the antiferromagnetic insulator and at finite temperatures and dopings.

Enhanced Electro-Static Modulation of Ionic Diffusion through Carbon Nanotube Membranes by Diazonium Grafting Chemistry

PubMed Central

Majumder, Mainak; Keis, Karin; Zhan, Xin; Meadows, Corey; Cole, Jeggan

2013-01-01

A membrane structure consisting of an aligned array of open ended carbon nanotubes (~ 7 nm i.d.) spanning across an inert polymer matrix allows the diffusive transport of aqueous ionic species through CNT cores. The plasma oxidation process that opens CNTs tips inherently introduces carboxylic acid groups at the CNT tips, which allows for a limited amount of chemical functional at the CNT pore entrance. However for numerous applications, it is important to increase the density of carboxylic acid groups at the pore entrance for effective separation processes. Aqueous diazonium based electro-chemistry significantly increases the functional density of carboxylic acid groups. pH dependent dye adsorption-desorption and interfacial capacitance measurements indicate ~ 5–6 times increase in functional density. To further control the spatial location of the functional chemistry, a fast flowing inert liquid column inside the CNT core is found to restrict the diazonium grafting to the CNT tips only. This is confirmed by the increased flux of positively charged Ru(bi-py)3+2 with anionic functionality. The electrostatic enhancement of ion diffusion is readily screened in 0.1(M) electrolyte solution consistent with the membrane pore geometry and increased functional density. PMID:25132719

Interface-Engineered Charge-Transport Properties in Benzenedithiol Molecular Electronic Junctions via Chemically p-Doped Graphene Electrodes.

PubMed

Jang, Yeonsik; Kwon, Sung-Joo; Shin, Jaeho; Jeong, Hyunhak; Hwang, Wang-Taek; Kim, Junwoo; Koo, Jeongmin; Ko, Taeg Yeoung; Ryu, Sunmin; Wang, Gunuk; Lee, Tae-Woo; Lee, Takhee

2017-12-06

In this study, we fabricated and characterized vertical molecular junctions consisting of self-assembled monolayers of benzenedithiol (BDT) with a p-doped multilayer graphene electrode. The p-type doping of a graphene film was performed by treating pristine graphene (work function of ∼4.40 eV) with trifluoromethanesulfonic (TFMS) acid, producing a significantly increased work function (∼5.23 eV). The p-doped graphene-electrode molecular junctions statistically showed an order of magnitude higher current density and a lower charge injection barrier height than those of the pristine graphene-electrode molecular junctions, as a result of interface engineering. This enhancement is due to the increased work function of the TFMS-treated p-doped graphene electrode in the highest occupied molecular orbital-mediated tunneling molecular junctions. The validity of these results was proven by a theoretical analysis based on a coherent transport model that considers asymmetric couplings at the electrode-molecule interfaces.

Local dark matter and dark energy as estimated on a scale of ~1 Mpc in a self-consistent way

NASA Astrophysics Data System (ADS)

Chernin, A. D.; Teerikorpi, P.; Valtonen, M. J.; Dolgachev, V. P.; Domozhilova, L. M.; Byrd, G. G.

2009-12-01

Context: Dark energy was first detected from large distances on gigaparsec scales. If it is vacuum energy (or Einstein's Λ), it should also exist in very local space. Here we discuss its measurement on megaparsec scales of the Local Group. Aims: We combine the modified Kahn-Woltjer method for the Milky Way-M 31 binary and the HST observations of the expansion flow around the Local Group in order to study in a self-consistent way and simultaneously the local density of dark energy and the dark matter mass contained within the Local Group. Methods: A theoretical model is used that accounts for the dynamical effects of dark energy on a scale of ~1 Mpc. Results: The local dark energy density is put into the range 0.8-3.7ρv (ρv is the globally measured density), and the Local Group mass lies within 3.1-5.8×1012 M⊙. The lower limit of the local dark energy density, about 4/5× the global value, is determined by the natural binding condition for the group binary and the maximal zero-gravity radius. The near coincidence of two values measured with independent methods on scales differing by ~1000 times is remarkable. The mass ~4×1012 M⊙ and the local dark energy density ~ρv are also consistent with the expansion flow close to the Local Group, within the standard cosmological model. Conclusions: One should take into account the dark energy in dynamical mass estimation methods for galaxy groups, including the virial theorem. Our analysis gives new strong evidence in favor of Einstein's idea of the universal antigravity described by the cosmological constant.

Current density characteristics in the studies of electromagnetically induced transparency in a GaAs/GaAlAs quantum well

NASA Astrophysics Data System (ADS)

Jayarubi, J.; Peter, A. John

2017-05-01

Confinement potential profiles due to conduction and valence bands are obtained in a Ga0.7Al0.3As/ GaAs/ Ga0.7Al0.3As using variation formulism. The free electron distribution is carried out. The confined energy eigenvalue and its corresponding wavefunctions of charge carriers are found using self-consistent method. The confined energies with the geometrical confinement are computed. The potentials due to charges are done by Poisson equation. The effects of dielectric mismatch between the GaAs and GaAlAs semiconductors are introduced in the effective potential expressions. Transfer matrix method is employed to obtain the respective energies. The transmission probability is obtained for a constant well size. The high current density characteristics as a function of applied voltage is investigated. This investigation on the electromagnetically induced transparency in the photonic material will exploit in fabricating novel nonlinear optical devices in future.

The radial gradients and collisional properties of solar wind electrons

NASA Technical Reports Server (NTRS)

Gilvie, K. W.; Scudder, J. D.

1977-01-01

The plasma instrument on Mariner 10 carried out measurements of electron density and temperature in the interplanetary medium between heliocentric distances of 0.85 and 0.45 AU. Due to the stable coronal configuration and low solar activity during the period of observation, the radial variations of these quantities could be obtained. The power-law exponent of the core temperature was measured to be -0.3 + or - 0.04, and the halo temperature was found to be almost independent of heliocentric distance. The exponent of the power law for the density variation was 2.5 + or - 0.2 and the extrapolated value at 1 AU was consistent with measured values during the same period. Calculations of the core electron self-collision time, and the core-halo equipartition time were made as a function of radial distance. These measurements indicate a macroscale picture of a Coulomb-collisional core and a collisionless isothermal halo. Extrapolating back to the sun, core and halo temperatures become equal at a radial distance of approx. 2-15 radii.

Quark-Meson-Coupling (QMC) model for finite nuclei, nuclear matter and beyond

NASA Astrophysics Data System (ADS)

Guichon, P. A. M.; Stone, J. R.; Thomas, A. W.

2018-05-01

The Quark-Meson-Coupling model, which self-consistently relates the dynamics of the internal quark structure of a hadron to the relativistic mean fields arising in nuclear matter, provides a natural explanation to many open questions in low energy nuclear physics, including the origin of many-body nuclear forces and their saturation, the spin-orbit interaction and properties of hadronic matter at a wide range of densities up to those occurring in the cores of neutron stars. Here we focus on four aspects of the model (i) a full comprehensive survey of the theory, including the latest developments, (ii) extensive application of the model to ground state properties of finite nuclei and hypernuclei, with a discussion of similarities and differences between the QMC and Skyrme energy density functionals, (iii) equilibrium conditions and composition of hadronic matter in cold and warm neutron stars and their comparison with the outcome of relativistic mean-field theories and, (iv) tests of the fundamental idea that hadron structure changes in-medium.

In Silico Modeling of Indigo and Tyrian Purple Single-Electron Nano-Transistors Using Density Functional Theory Approach

NASA Astrophysics Data System (ADS)

Shityakov, Sergey; Roewer, Norbert; Förster, Carola; Broscheit, Jens-Albert

2017-07-01

The purpose of this study was to develop and implement an in silico model of indigoid-based single-electron transistor (SET) nanodevices, which consist of indigoid molecules from natural dye weakly coupled to gold electrodes that function in a Coulomb blockade regime. The electronic properties of the indigoid molecules were investigated using the optimized density-functional theory (DFT) with a continuum model. Higher electron transport characteristics were determined for Tyrian purple, consistent with experimentally derived data. Overall, these results can be used to correctly predict and emphasize the electron transport functions of organic SETs, demonstrating their potential for sustainable nanoelectronics comprising the biodegradable and biocompatible materials.

A review on ab initio studies of static, transport, and optical properties of polystyrene under extreme conditions for inertial confinement fusion applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collins, L. A.; Boehly, T. R.; Ding, Y. H.

Polystyrene (CH), commonly known as “plastic,” has been one of the widely used ablator materials for capsule designs in inertial confinement fusion (ICF). Knowing its precise properties under high-energy-density conditions is crucial to understanding and designing ICF implosions through radiation–hydrodynamic simulations. For this purpose, systematic ab initio studies on the static, transport, and optical properties of CH, in a wide range of density and temperature conditions (ρ= 0.1 to 100 g/cm 3 and T = 10 3 to 4 × 10 6K), have been conducted using quantum molecular dynamics (QMD) simulations based on the density functional theory. We have builtmore » several wide-ranging, self-consistent material-properties tables for CH, such as the first-principles equation of state (FPEOS), the QMD-based thermal conductivity (Κ QMD) and ionization, and the first-principles opacity table (FPOT). This paper is devoted to providing a review on (1) what results were obtained from these systematic ab initio studies; (2) how these self-consistent results were compared with both traditional plasma-physics models and available experiments; and (3) how these first-principles–based properties of polystyrene affect the predictions of ICF target performance, through both 1-D and 2-D radiation–hydrodynamic simulations. In the warm dense regime, our ab initio results, which can significantly differ from predictions of traditional plasma-physics models, compared favorably with experiments. When incorporated into hydrocodes for ICF simulations, these first-principles material properties of CH have produced significant differences over traditional models in predicting 1-D/2-D target performance of ICF implosions on OMEGA and direct-drive–ignition designs for the National Ignition Facility. Lastly, we will discuss the implications of these studies on the current small-margin ICF target designs using a CH ablator.« less

A review on ab initio studies of static, transport, and optical properties of polystyrene under extreme conditions for inertial confinement fusion applications

DOE PAGES

Collins, L. A.; Boehly, T. R.; Ding, Y. H.; ...

2018-03-23

Polystyrene (CH), commonly known as “plastic,” has been one of the widely used ablator materials for capsule designs in inertial confinement fusion (ICF). Knowing its precise properties under high-energy-density conditions is crucial to understanding and designing ICF implosions through radiation–hydrodynamic simulations. For this purpose, systematic ab initio studies on the static, transport, and optical properties of CH, in a wide range of density and temperature conditions (ρ= 0.1 to 100 g/cm 3 and T = 10 3 to 4 × 10 6K), have been conducted using quantum molecular dynamics (QMD) simulations based on the density functional theory. We have builtmore » several wide-ranging, self-consistent material-properties tables for CH, such as the first-principles equation of state (FPEOS), the QMD-based thermal conductivity (Κ QMD) and ionization, and the first-principles opacity table (FPOT). This paper is devoted to providing a review on (1) what results were obtained from these systematic ab initio studies; (2) how these self-consistent results were compared with both traditional plasma-physics models and available experiments; and (3) how these first-principles–based properties of polystyrene affect the predictions of ICF target performance, through both 1-D and 2-D radiation–hydrodynamic simulations. In the warm dense regime, our ab initio results, which can significantly differ from predictions of traditional plasma-physics models, compared favorably with experiments. When incorporated into hydrocodes for ICF simulations, these first-principles material properties of CH have produced significant differences over traditional models in predicting 1-D/2-D target performance of ICF implosions on OMEGA and direct-drive–ignition designs for the National Ignition Facility. Lastly, we will discuss the implications of these studies on the current small-margin ICF target designs using a CH ablator.« less

Reversible near-infrared light directed reflection in a self-organized helical superstructure loaded with upconversion nanoparticles.

PubMed

Wang, Ling; Dong, Hao; Li, Yannian; Xue, Chenming; Sun, Ling-Dong; Yan, Chun-Hua; Li, Quan

2014-03-26

Adding external, dynamic control to self-organized superstructures with desired functionalities is an important leap necessary in leveraging the fascinating molecular systems for applications. Here, the new light-driven chiral molecular switch and upconversion nanoparticles, doped in a liquid crystal media, were able to self-organize into an optically tunable helical superstructure. The resulting nanoparticle impregnated helical superstructure was found to exhibit unprecedented reversible near-infrared (NIR) light-guided tunable behavior only by modulating the excitation power density of a continuous-wave NIR laser (980 nm). Upon irradiation by the NIR laser at the high power density, the reflection wavelength of the photonic superstructure red-shifted, whereas its reverse process occurred upon irradiation by the same laser but with the lower power density. Furthermore, reversible dynamic NIR-light-driven red, green, and blue reflections in a single thin film, achieved only by varying the power density of the NIR light, were for the first time demonstrated.

Mode coupling theory for nonequilibrium glassy dynamics of thermal self-propelled particles.

PubMed

Feng, Mengkai; Hou, Zhonghuai

2017-06-28

We present a mode coupling theory study for the relaxation and glassy dynamics of a system of strongly interacting self-propelled particles, wherein the self-propulsion force is described by Ornstein-Uhlenbeck colored noise and thermal noises are included. Our starting point is an effective Smoluchowski equation governing the distribution function of particle positions, from which we derive a memory function equation for the time dependence of density fluctuations in nonequilibrium steady states. With the basic assumption of the absence of macroscopic currents and standard mode coupling approximation, we can obtain expressions for the irreducible memory function and other relevant dynamic terms, wherein the nonequilibrium character of the active system is manifested through an averaged diffusion coefficient D[combining macron] and a nontrivial structural function S 2 (q) with q being the magnitude of wave vector q. D[combining macron] and S 2 (q) enter the frequency term and the vertex term for the memory function, and thus influence both the short time and the long time dynamics of the system. With these equations obtained, we study the glassy dynamics of this thermal self-propelled particle system by investigating the Debye-Waller factor f q and relaxation time τ α as functions of the persistence time τ p of self-propulsion, the single particle effective temperature T eff as well as the number density ρ. Consequently, we find the critical density ρ c for given τ p shifts to larger values with increasing magnitude of propulsion force or effective temperature, in good accordance with previously reported simulation work. In addition, the theory facilitates us to study the critical effective temperature T for fixed ρ as well as its dependence on τ p . We find that T increases with τ p and in the limit τ p → 0, it approaches the value for a simple passive Brownian system as expected. Our theory also well recovers the results for passive systems and can be easily extended to more complex systems such as active-passive mixtures.

Self-consistent Model of Magnetospheric Electric Field, RC and EMIC Waves

NASA Technical Reports Server (NTRS)

Gamayunov, K. V.; Khazanov, G. V.; Liemohn, M. W.; Fok, M.-C.

2007-01-01

Electromagnetic ion cyclotron (EMIC) waves are an important magnetospheric emission, which is excited near the magnetic equator with frequencies below the proton gyro-frequency. The source of bee energy for wave growth is provided by temperature anisotropy of ring current (RC) ions, which develops naturally during inward convection from the plasma sheet These waves strongly affect the dynamic s of resonant RC ions, thermal electrons and ions, and the outer radiation belt relativistic electrons, leading to non-adiabatic particle heating and/or pitch-angle scattering and loss to the atmosphere. The rate of ion and electron scattering/heating is strongly controlled by the Wave power spectral and spatial distributions, but unfortunately, the currently available observational information regarding EMIC wave power spectral density is poor. So combinations of reliable data and theoretical models should be utilized in order to obtain the power spectral density of EMIC waves over the entire magnetosphere throughout the different storm phases. In this study, we present the simulation results, which are based on two coupled RC models that our group has developed. The first model deals with the large-scale magnetosphere-ionosphere electrodynamic coupling, and provides a self-consistent description of RC ions/electrons and the magnetospheric electric field. The second model is based on a coupled system of two kinetic equations, one equation describes the RC ion dynamics and another equation describes the power spectral density evolution of EMIC waves, and self-consistently treats a micro-scale electrodynamic coupling of RC and EMIC waves. So far, these two models have been applied independently. However, the large-scale magnetosphere-ionosphere electrodynamics controls the convective patterns of both the RC ions and plasmasphere altering conditions for EMIC wave-particle interaction. In turn, the wave induced RC precipitation Changes the local field-aligned current distributions and the ionospheric conductances, which are crucial for a large-scale electrodynamics. The initial results from this new self-consistent model of the magnetospheric electric field, RC and EMIC waves will be shown in this presentation.

Proximity effects in ferromagnet-superconductor structures

NASA Astrophysics Data System (ADS)

Halterman, Klaus Byron

I present an extensive theoretical investigation of the proximity effects that occur in ferromagnet/superconductor systems. I use a numerical method to solve self consistently the Bogoliubov-de Gennes equations in the continuum. I obtain the pair amplitude and the local density of states (DOS), and use these results to extract the relevant lengths characterizing both the leakage of superconductivity into the magnet and to study spin splitting induced in the superconductor. These phenomena are investigated as a function of parameters such as temperature, magnet polarization, interfacial scattering, sample size and Fermi wave vector mismatch, all of which turn out to have an important influence on the results. These comprehensive results should help characterize and analyze future data, and are shown to be in agreement with existing experiments.

Application of an extended random-phase approximation to giant resonances in light-, medium-, and heavy-mass nuclei

NASA Astrophysics Data System (ADS)

Tselyaev, V.; Lyutorovich, N.; Speth, J.; Krewald, S.; Reinhard, P.-G.

2016-09-01

We present results of the time blocking approximation (TBA) for giant resonances in light-, medium-, and heavy-mass nuclei. The TBA is an extension of the widely used random-phase approximation (RPA) adding complex configurations by coupling to phonon excitations. A new method for handling the single-particle continuum is developed and applied in the present calculations. We investigate in detail the dependence of the numerical results on the size of the single-particle space and the number of phonons as well as on nuclear matter properties. Our approach is self-consistent, based on an energy-density functional of Skyrme type where we used seven different parameter sets. The numerical results are compared with experimental data.

On the theory of quantum measurement

NASA Technical Reports Server (NTRS)

Haus, Hermann A.; Kaertner, Franz X.

1994-01-01

Many so called paradoxes of quantum mechanics are clarified when the measurement equipment is treated as a quantized system. Every measurement involves nonlinear processes. Self consistent formulations of nonlinear quantum optics are relatively simple. Hence optical measurements, such as the quantum nondemolition (QND) measurement of photon number, are particularly well suited for such a treatment. It shows that the so called 'collapse of the wave function' is not needed for the interpretation of the measurement process. Coherence of the density matrix of the signal is progressively reduced with increasing accuracy of the photon number determination. If the QND measurement is incorporated into the double slit experiment, the contrast ratio of the fringes is found to decrease with increasing information on the photon number in one of the two paths.

Probing Phase Evolutions of Au-Methyl-Propyl-Thiolate Self-Assembled Monolayers on Au(111) at the Molecular Level.

PubMed

Gao, Jianzhi; Lin, Haiping; Qin, Xuhui; Zhang, Xin; Ding, Haoxuan; Wang, Yitao; Rokni Fard, Mahroo; Kaya, Dogan; Zhu, Gangqiang; Li, Qing; Li, Youyong; Pan, Minghu; Guo, Quanmin

2018-06-18

A self-assembled monolayer (SAM) consisting of a mixture of CH 3 S-Au-SCH 3 , CH 3 S-Au-S(CH 2 ) 2 CH 3 , and CH 3 (CH 2 ) 2 S-Au-S(CH 2 ) 2 CH 3 was studied systematically using scanning tunneling microscopy and density functional calculations. We find that the SAM is subjected to frequent changes at the molecular level on the time scale of ∼minutes. The presence of CH 3 S or CH 3 S-Au as a dissociation product of CH 3 S-Au-SCH 3 plays a key role in the dynamical behavior of the mixed SAM. Slow phase separation takes place at room temperature over hours to days, leading to the formation of methyl-thiolate-rich and propyl-thiolate-rich phases. Our results provide new insights into the chemistry of the thiolate-Au interface, especially for ligand exchange reaction in the RS-Au-SR staple motif.

On effective temperature in network models of collective behavior

DOE Office of Scientific and Technical Information (OSTI.GOV)

Porfiri, Maurizio, E-mail: mporfiri@nyu.edu; Ariel, Gil, E-mail: arielg@math.biu.ac.il

Collective behavior of self-propelled units is studied analytically within the Vectorial Network Model (VNM), a mean-field approximation of the well-known Vicsek model. We propose a dynamical systems framework to study the stochastic dynamics of the VNM in the presence of general additive noise. We establish that a single parameter, which is a linear function of the circular mean of the noise, controls the macroscopic phase of the system—ordered or disordered. By establishing a fluctuation–dissipation relation, we posit that this parameter can be regarded as an effective temperature of collective behavior. The exact critical temperature is obtained analytically for systems withmore » small connectivity, equivalent to low-density ensembles of self-propelled units. Numerical simulations are conducted to demonstrate the applicability of this new notion of effective temperature to the Vicsek model. The identification of an effective temperature of collective behavior is an important step toward understanding order–disorder phase transitions, informing consistent coarse-graining techniques and explaining the physics underlying the emergence of collective phenomena.« less

Catalytic and Thermal 1,2-Rearrangement of (α-Mercaptobenzyl)trimethylsilane

NASA Astrophysics Data System (ADS)

Zhang, Jie; Cui, Mengzhong; Feng, Shengyu; Sun, Xiaomin; Feng, Dacheng

2009-09-01

The mechanisms of catalytic and thermal 1,2-rearrangement of (α-mercaptobenzyl)trimethylsilane were studied by using density functional theory (DFT) at the MP2/6-31+G(d,p)//B3LYP/6-31G(d) levels. The results show that (α-mercaptobenzyl)trimethylsilane rearranges to (benzylthio)trimethylsilane through a trimethylsilyl group migration from C to S atom via a transition state of pentacoordinate Si atom with or without radical initiators. The low reaction activation energy (15.1 kcal/mol) is responsible for the fast rearrangement in the presence of radical initiators. Both radical and nonradical thermal rearrangement mechanisms were suggested, and the radical mechanism dominates through its self-catalyzing. These results are consistent with the experiment results. The activation energy (ΔHact = 15.1 kcal/mol) for the rate-determining step within the self-catalytic cycle is low enough to make (trimethylsilylbenzyl)thiyl radical be a reasonable catalyst for the thermal rearrangement. The catalytic and thermal 1,2-rearrangement mechanisms of (α-mercaptobenzyl)trimethylsilane, especially the self-catalytic radical mechanism, were revealed for the first time. The comparison of the rearrangement mechanisms between (α-mercaptobenzyl)trimethylsilane and silylmethanethiol discloses the factors in determining the reaction mechanism of such kinds of mercaptoalkyl-functionalized organosilanes. The phenyl group is found to be favorable for the radical rearrangement, thus making (α-mercaptobenzyl)trimethylsilane instable.