Spin-orbit interactions in electronic structure quantum Monte Carlo methods
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Melton, Cody A.↗
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Improved unconstrained energy functional method for eigensolvers in electronic structure calculations
This paper reports on the performance of a preconditioned conjugate gradient based iterative eigensolver using an unconstrained energy functional minimization scheme. In contrast to standard implementations, this scheme avoids an explicit reorthogonalization of the trial eigenvectors and becomes an attractive alternative for the solution of very large problems. The unconstrained formulation is implemented in the first-principles materials and chemistry CP2K code, which performs electronic structure calculations based on a density functional theory approximation to the solution of the many-body Schrödinger equation. We study the convergence of the unconstrained formulation, as well as its parallel scaling, on a Cray XC40 at the National Energy Research Scientific Computing Center (NERSC). The systems we use in our studies are bulk liquid water, a supramolecular catalyst gold(III)-complex, a bilayer of MoS2-WSe2 and a divacancy point defect in silicon, with the number of atoms ranging from 2,247 to 12,288. We show that the unconstrained formulation with an appropriate preconditioner has good convergence properties and scales well to 230k cores, roughly 38% of the full machine.
Del Ben, M↗
The high-valent vanadium chemistry of isoindoline chelates
Isoindoline-based chelates, in particular bis(arylimino)isoindolines, have shown extensive metal binding chemistry. Although this chemistry has been explored for the middle and late transition metal ions, little work has been carried out on early transition metal complexes. In this article, we present the first examples of vanadium coordinated using four bis(arylimino)isoindolines, in which the aryl groups are pyrazole, indazole, benzimidazole, and pyridine (ligands 1–4 , respectively). We isolated five complexes using vanadyl sulfate or vanadyl acetylacetonate as the vanadium source. In all cases, the ligands bound in a meridional mode, and for four of the complexes, the vanadium ion was observed in the V(v) oxidation state. Three of the ligands ( 1–3 ) formed VO 2 complexes with vanadyl sulfate and vanadyl acetylacetonate, but the bis(pyridylimino)isoindoline (ligand 4 ) formed a V(v) oxosulfonato complex with the former starting material and a vanadyl V(iv) acetylacetonate with the latter starting material. All metal compounds were structurally elucidated by X-ray crystallographic methods, and we probed their electronic structures using DFT methods.
Bore, Joan C. [Univ. of Akron, OH (United States)]↗
Half-metallic Ferromagnetism in Novel Rh{sub 2}-based Full-Heusler Alloys Rh{sub 2}FeZ (Z = Ga and In)
In this approach, we have employed the ab initio method of full-potential linearized plane waves plus local orbital based on the framework of density functional theory, within the spin generalized gradient approximation plus U (GGA+U), where U is the Hubbard correlation term for exchange-correlation potential. This method is used to predict the equilibrium structural parameters, the electronic structure, and the magnetic properties of Rh{sub 2}FeGa and Rh{sub 2}FeIn full-Heusler alloys. The structural properties result show that both Rh{sub 2}FeGa and Rh{sub 2}FeIn compounds are stable in ferromagnetic states. The spin-polarized electronic structure demonstrate that both full-Heusler compounds are half-metals with half-metallic band gap (E{sub HM}) of 0.326 eV for Rh{sub 2}FeGa alloy and 0.245 eV for Rh{sub 2}FeIn alloy, where the apparition of an indirect gap from Γ to X in minority spin is shown by these Heusler alloys. Furthermore, calculations of total magnetic moment give the value of 5 µ{sub B}, which agrees with Slater-Pauling rule; also, the atomic magnetic moment of both Rh and Fe transition metals have the same sign which depicts the ferromagnetic behavior.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Potential existence of post-perovskite nitrides; DFT studies of ThTaN{sub 3}
Within density functional theory, the equations of state for cubic perovskite (c-PV) and hypothetic orthorhombic perovskite (o-PV GdFeO{sub 3}-type) and post-perovskite (PPV) forms of ThTaN{sub 3} are obtained. The decreasing volume and stabilizing energy indicate pressure enabled transitions: c-PV ->o-PV ->PPV. From electronic structure analysis the chemical system is found insulating in the c-PV ground state form with {approx}1eV band gap and semi-conducting for the PPV due to increased covalence. The chemical bonding properties show that Th and Ta bondings with the 2 N sites are selectively differentiated and reinforced for Ta-N bond within PPV form. This is the consequence of the corner as well as edge sharing octahedra characterizing PPV while PV structures have only corner sharing octahedra. It is the first case of potential post-perovskite nitride. - ThTaN{sub 3}: Projected charge density (for 4 fu) onto basal plane: (a) cubic perovskite, (b) orthorhombic perovskite and (c) post-perovskite. Red, green and blue areas are relevant to strong, medium and low localization of density.
36 MATERIALS SCIENCE↗
First-Principle Calculation of Electronic Structures and Magnetic Properties of Heusler Alloys Co{sub 2}ZrPb and Zr{sub 2}MnBa
Using first-principle method of density functional theory (DFT), we have investigated the underlying mechanism related to the electronic and magnetic properties of novel full Heusler alloys Co{sub 2}ZrPb and Zr{sub 2}MnB. Our results show that compound Zr{sub 2}MnB is a nonmagnetic semiconductor whereas Co{sub 2}ZrPb is half metallic a magnetic moment of 2 μ{sub B} per formula unit. It exhibits a large spin gap of 0.334 eV for equilibrium lattice constant and has excellent half-metallic ferrimagnetism with 100% spin polarization at the Fermi level. The half-metallicity of Co{sub 2}ZrPb is stable against lattice change of −2.6 to 0.83%. The Co-based Heusler alloys are expected to be ideal candidates for spintronic devices.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Effects of the preparation processes on structural, electronic, and optical properties of LaHoO{sub 3}
Highlights: • The preparation of LaHoO{sub 3} by combustion and hydrothermal techniques was performed. • The crystal structure and characterization of the synthesized oxides were carried out. • The lattice distortions have effects on Raman, luminescence and optical band gap. • Electronic properties and band structure have been carried out by DFT method. • Sample prepared by hydrothermal process gives higher emission intensities. - ABSTRACT: Lanthanum holmium oxide (LaHoO{sub 3}) was synthesized using combustion and hydrothermal processes in order to compare the effects of preparation method on structural, electronic, and optical properties. For this purpose, the as-prepared samples were characterized with infrared spectroscopy, Raman scattering, X-ray diffraction, and scanning electronic microscopy. The Rietveld refinements structure of as-prepared samples show that lattice distortions and volume expansion were obtained for LaHoO{sub 3} synthesized with hydrothermal method compared to combustion process. The luminescence properties were investigated upon 488 and 750 nm laser excitations. The emission curves show the presence of characteristic Ho{sup 3+} transitions with a higher emission intensity for a sample prepared by hydrothermal method than the one obtained by combustion process. The structures properties effects on the band structure and the density of states were realized via generalized gradient approximation functional with Hubbard correction. The lattice distortions were found to have effects on Raman, luminescence and optical band gap.
36 MATERIALS SCIENCE↗
Electronic properties of graphene nanoribbons: A density functional investigation
Density functional theory calculations have been performed on graphene nano ribbons (GNRs) to investigate the electronic properties as a function of chirality, size and hydrogenation on the edges. The calculations were performed on GNRs with armchair and zigzag configurations with 28, 34, 36, 40, 50, 56, 62, 66 carbon atoms. The structural stability of AGNR and ZGNR increases with the size of nanoribbon where as hydrogenation of GNR tends to lowers their structural stability. All GNRs considered have shown semiconducting behavior with HOMO-LUMO gap decreasing with the increase in the GNR size. The hydrogenation of GNR decreases its HOMO-LUMO gap significantly. The results are in agreement with the available experimental and theoretical results.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
In situ investigations of laser and thermally modified As{sub 2}S{sub 3} nanolayers: Synchrotron radiation photoelectron spectroscopy and density functional theory calculations
As-deposited, annealed, and in situ As{sub 2}S{sub 3} nanolayers, illuminated by blue (405 nm) and red (650 nm) laser light, were studied using synchrotron radiation photoelectron spectroscopy and DFT electronic structure calculations. Changes in composition and local atomic coordination occurring in the irradiated region of As{sub 2}S{sub 3} films were monitored by analysis of As 3d and S 2p core levels. These studies show that both the thermal treatment and the red laser illumination of As{sub 2}S{sub 3} nanolayers decrease the concentration of homopolar (As-As and S-S) bonds. From the other hand, an increasing concentration of As-rich structural units (s.u.) with a homopolar As-As bond was observed under in situ blue laser illumination of As{sub 2}S{sub 3} nanolayers. Molecular orbital energies were calculated for different As- and S-centered s.u. and used for the interpretation of the core levels and valence band spectra. The surface local structure of the As{sub 2}S{sub 3} nanolayers and its photoinduced transformation are discussed in detail.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Comparison of Conjugate Gradient Density Matrix Search and Chebyshev Expansion Methods for Avoiding Diagonalization in Large-Scale Electronic Structure Calculations
We report a comparison of two linear-scaling methods which avoid the diagonalization bottleneck of traditional electronic structure algorithms. The Chebyshev expansion method (CEM) is implemented for carbon tight-binding calculations of large systems and its memory and timing requirements compared to those of our previously implemented conjugate gradient density matrix search (CG-DMS). Benchmark calculations are carried out on icosahedral fullerenes from C60 to C8640 and the linear scaling memory and CPU requirements of the CEM demonstrated. We show that the CPU requisites of the CEM and CG-DMS are similar for calculations with comparable accuracy.
Bates, Kevin R.↗
Density functional theory study of Fe{sub 3}Ga
First-principles scalar relativistic calculations in supercells of 16 atoms are used to represent disordered B2 ordering of Fe{sub 3}Ga in order to observe the effect of Ga-Ga pairs on the electronic structure of this alloy. From a comparison with pure bcc Fe it is observed that the energy position and occupation of e{sub g} and t{sub 2g} states are largely affected by the Ga-Ga pairs and strengthened intraplane interactions takes place. The results show that a larger hybridization of the conduction band is in the source of the magnetostriction enhancement experimentally observed in Galfenol.
36 MATERIALS SCIENCE↗
Structural and electronic properties of Au{sub n−x}Pt{sub x} (n = 2–14; x ⩽ n) clusters: The density functional theory investigation
The structural evolutions and electronic properties of bimetallic Au{sub n–x}Pt{sub x} (n = 2–14; x ⩽ n) clusters are investigated by using the density functional theory (DFT) with the generalized gradient approximation (GGA). The monatomic doping Au{sub n–1}Pt clusters are emphasized and compared with the corresponding pristine Au{sub n} clusters. The results reveal that the planar configurations are favored for both Au{sub n–1}Pt and Au{sub n} clusters with size up to n = 13, and the former often employ the substitution patterns based on the structures of the latter. The most stable clusters are Au{sub 6} and Au{sub 6}Pt, which adopt regular planar triangle (D{sub 3h}) and hexagon-ring (D{sub 6h}) structures and can be regarded as the preferential building units in designing large clusters. For Pt-rich bimetallic clusters, their structures can be obtained from the substitution of Pt atoms by Au atoms from the Pt{sub n} structures, where Pt atoms assemble together and occupy the center yet Au atoms prefer the apex positions showing a segregation effect. With respect to pristine Au clusters, Au{sub n}Pt clusters exhibit somewhat weaker and less pronounced odd-even oscillations in the highest occupied and lowest unoccupied molecular-orbital gaps (HOMO-LUMO gap), electron affinity (EA), and ionization potential (IP) due to the partially released electron pairing effect. The analyses of electronic structure indicate that Pt atoms in AuPt clusters would delocalize their one 6s and one 5d electrons to contribute the electronic shell closure. The sp-d hybridizations as well as the d-d interactions between the host Au and dopant Pt atoms result in the enhanced stabilities of AuPt clusters.
36 MATERIALS SCIENCE↗
Interstitial and substitutional zirconium in SrTiO3
We investigate Zr in SrTiO3 (STO) as a model for nuclear waste forms in which the fission product Sr90 eventually decays to stable Zr through beta emission. The transformation of a divalent into a tetravalent constituent is expected to affect the long-term structural and chemical stability of this solid. Computational methods of electronic structure theory, specifically the density functional theory (DFT) within the supercell model, are used to predict the thermodynamic stability and electronic states of interstitial and Sr- or Ti-substituted Zr atoms in the STO lattice. Native defects such as vacancies and antisites are also considered. When Zr replaces Sr, its most stable configuration is to simply occupy the Sr site (instead of, for example, replacing a Ti and displacing the Ti to the Sr site.) For Zr added to the lattice, its most stable configuration is to replace a Ti, making a ZrTi impurity plus a Ti interstitial (as opposed to the Zr just remaining as an interstitial atom.) ZrSr is predicted to be a double electron donor, ZrTi is electrically inactive and interstitial Zr and Ti are predicted to be quadruple donors, with all donor levels in the conduction band. ZrSr and the tetravalent interstitials are all predicted to increase the crystal volume, and the interstitials also are predicted to lead to a tetragonal distortion of the lattice. Experiments with injection of Zr atoms into STO qualitatively confirm these predictions of crystal structural changes.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Full-dimensional multi-state simulation of the photodissociation of thioanisole
The photodissociation of thioanisole is very interesting because the experiments of Lim and Kim provide evidence for mode-specific effects on the product distribution. They showed that, with a specific S–CH 3 stretching mode being excited as the reagent is excited to the S 1 electronic state, there is a sharp increase in the proportion of the ground-state product to the excited-state product. In this work, we report 78 011 full-dimensional semiclassical multi-state trajectories of the photodissociation process using the coherent switching with decay of mixing dynamics method. The potential surfaces and couplings are based on electronic structure calculations that include dynamic correlation through second order perturbation theory. We report results for four sets of initial conditions, one corresponding roughly to 0–0 excitation and three corresponding to exciting one vibrational mode, to look for mode-specific effects. The simulations show no significant mode-specific effect on the product energy distributions, but they do show an effect on the distribution of minimum-energy gaps in the trajectories and on the lifetime for dissociation. In particular, excitation of the S–CH 3 stretching mode leads to trajectories passing closer to the S 1 -S 2 conical intersection and to shorter lifetimes. This provides a possible explanation of why experimental results are different for excitation of this vibration
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Analysis of the electronic structure of ZrO{sub 2} by Compton spectroscopy
The electronic structure of ZrO{sub 2} is studied using the Compton scattering technique. The first-ever Compton profile measurement on polycrystalline ZrO{sub 2} was obtained using 59.54 keV gamma-rays emanating from the {sup 241}Am radioisotope. To explain the experimental data, we compute theoretical Compton profile values using the method of linear combination of atomic orbitals in the framework of density functional theory. The correlation scheme proposed by Perdew-Burke-Ernzerhof and the exchange scheme of Becke are considered. The ionic-model-based calculations for a number of configurations, i.e., Zr{sup +x}(O{sup -x/2}){sub 2} (0 {<=} x {<=} 2), are also performed to estimate the charge transfer on compound formation, and the study supports transfer of 1.5 electrons from Zr to O atoms.
36 MATERIALS SCIENCE↗
Time-dependent quantum chemistry of laser driven many-electron molecules
A Time-Dependent Configuration Interaction approach using multiple Feshbach partitionings, corresponding to multiple ionization stages of a laser-driven molecule, has recently been proposed [T.-T. Nguyen-Dang and J. Viau-Trudel, J. Chem. Phys. 139, 244102 (2013)]. To complete this development toward a fully ab-initio method for the calculation of time-dependent electronic wavefunctions of an N-electron molecule, we describe how tools of multiconfiguration quantum chemistry such as the management of the configuration expansion space using Graphical Unitary Group Approach concepts can be profitably adapted to the new context, that of time-resolved electronic dynamics, as opposed to stationary electronic structure. The method is applied to calculate the detailed, sub-cycle electronic dynamics of BeH{sub 2}, treated in a 3–21G bound-orbital basis augmented by a set of orthogonalized plane-waves representing continuum-type orbitals, including its ionization under an intense λ = 800 nm or λ = 80 nm continuous-wave laser field. The dynamics is strongly non-linear at the field-intensity considered (I ≃ 10{sup 15} W/cm{sup 2}), featuring important ionization of an inner-shell electron and strong post-ionization bound-electron dynamics.
74 ATOMIC AND MOLECULAR PHYSICS↗
Structure-property relations in amorphous carbon for photovoltaics
Carbon is emerging as a material with great potential for photovoltaics (PV). However, the amorphous form (a-C) has not been studied in detail as a PV material, even though it holds similarities with amorphous Silicon (a-Si) that is widely employed in efficient solar cells. In this work, we correlate the structure, bonding, stoichiometry, and hydrogen content of a-C with properties linked to PV performance such as the electronic structure and optical absorption. We employ first-principles molecular dynamics and density functional theory calculations to generate and analyze a set of a-C structures with a range of densities and hydrogen concentrations. We demonstrate that optical and electronic properties of interest in PV can be widely tuned by varying the density and hydrogen content. For example, sunlight absorption in a-C films can significantly exceed that of a same thickness of a-Si for a range of densities and H contents in a-C. Our results highlight promising features of a-C as the active layer material of thin-film solar cells.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Crystallographic, magnetic, and electronic structures of ferromagnetic shape memory alloys Ni{sub 2}XGa (X=Mn,Fe,Co) from first-principles calculations
The crystallographic, magnetic and electronic structures of the ferromagnetic shape memory alloys Ni{sub 2}XGa (X=Mn, Fe, and Co), are systematically investigated by means of the first-principles calculations within the framework of density functional theory using the VIENNA AB INITIO SOFTWARE PACKAGE. The lattice parameters of both austenitic and martensitic phases in Ni{sub 2}MnGa have been calculated. The formation energies of the cubic phase of Ni{sub 2}XGa are estimated, and show a destabilization tendency if Mn atom is substituted by Fe or Co. From Ni{sub 2}MnGa to Ni{sub 2}CoGa, the down spin total density of states (DOS) at Fermi level is gradually increasing, whereas that of the up spin part remains almost unchanged. This is the main origin of the difference of the magnetic moment in these alloys. The partial DOS is dominated by the Ni and Mn 3d states in the bonding region below E{sub F}. There are two bond types existing in Ni{sub 2}XGa: one is between neighboring Ni atoms in Ni{sub 2}MnGa; the other is between Ni and X atoms in Ni{sub 2}FeGa and Ni{sub 2}CoGa alloys.
36 MATERIALS SCIENCE↗