Elastic anisotropy of OsB2 and RuB2 from first-principles study

The elastic anisotropy of the potential low compressible and hard materials OsB2 and RuB2 were studied by first-principles investigation within density functional theory. The structure, elastic constants, bulk modulus, shear modulus, Poisson's ratio and Debye temperature have been calculated within both local density approximation (LDA) and generalized gradient approximation (GGA). The results indicated that the calculated bulk modulus and shear modulus were in good agreement with the experimental and previous theoretical studies.

Structural stability and magnetic coupling in CaCu3Co4O12 from first principles

The structural, electronic and magnetic properties of CaCu3Co4O12 were studied by use of the full-potential linearized augmented plane wave method. The calculated results indicate that CaCu3Co4O12 is stable both thermodynamically and mechanically. Both GGA (generalized gradient approximation) and GGA + U methods predict that CaCu3Co4O12 is metallic. The ferromagnetic configuration is only slightly more stable in energy compared with the non-magnetic configuration (3.7 meV), suggesting that they are competitive for being the ground state. Co is in the low spin state (S = 1/2).

Ferrimagnetic and semiconducting CaCu3Fe2Sb2O12 by first principles

CaCu3Fe2Sb2O12 is mechanically stable, thermodynamically stable at pressures above 18 GPa. Both GGA and GGA + U methods predict that it is a ferrimagnetic semiconductor with Fe3+ in high spin state (S = 5/2). The coupling of Fe-Cu is antiferromagnetic, while that of Cu-Cu is ferromagnetic. The calculated total spin moment is 6.17 mu(B).

First principles investigation on the structural, mechanical and electronic properties of OsC2

The structural, mechanical and electronic properties Of OsC2 were investigated by use of the density functional theory. Seven structures were considered, i.e., orthorhombic Cmca (No. 12, OsSi2), Pmmn (No. 59, 002) and Pnnm (No. 58, OsN2); tetragonal P4(2)/mnm (No. 136, OsO2) and 14/mmm (No. 139, CaC2); cubic Fm-3m (No. 225, CaF2) and Pa-3 (No. 205, PtN2). The results indicate that Cmca in OsSi2 type structure is energetically the most stable phase among the considered structures. It is also stable mechanically. OsC2 in Pmmn phase has the largest bulk modulus 319 GPa and shear modulus 194 GPa. The elastic anisotropy is discussed. (C) 2009 Elsevier B.V. All rights reserved.

Electronic and magnetic properties of the monoclinic phase BiCrO3 from first-principles studies

Based on density functional theory, we systematically studied the electronic and magnetic properties of the real experimental structural phase BiCrO3 with the space group C2/c. It is found that the ground state is a moderately correlated Mott-Hubbard insulator with G-type antiferromagnetic structure, which is in agreement with the experimental observations. The magnetism can be qualitatively understood in terms of the superexchange mechanism via Cr1(t(2g))-O 2p-Cr-2(t(2g)). Moreover, the total energies calculated for various magnetic orderings lead to an estimate of the magnetic interaction constants.

First-principles study on the conducting mechanism of the heavy-fermion system CaCu3Ru4O12

We investigated the electronic structure of the d-electron heavy-fermion system CaCu3Ru4O12 by use of the full-potential linearized augmented plane wave method. Our results indicate that the compound is a paramagnetic metal, in agreement with the experimental observation. The conductivity of the compound is governed by two main factors. One is the Ru-O dp pi coupling around the Fermi energy level, which makes Ru-O-Ru networks conductive. The other is the hybridization between the itinerant Ru 4d electrons and the localized Cu 3d (dz(2) and part of dx(2)-y(2) and dxy) electrons through O 2p orbitals in the energy region from -2.0 to -1.0 eV. The Ru-O-Cu interaction makes the localized Cu electrons start to be itinerant through the coupling with Ru 4d electrons. This results in Ru-O-Cu networks being conductive. Therefore, in the title compound, both Ru-O-Ru and Ru-O-Cu networks contribute to the conducting behavior.

Ferrimagnetic and half-metallic CaCu3Fe4O12: Prediction from first principles investigation

The structural stability and physical properties of CaCu3Fe4O12 were studied by the use of the full-potential linearized augmented plane wave method. The authors' calculated result indicates that the title compound is stable both thermodynamically and mechanically. It is ferrimagnetic and half-metallic. The calculated magnetic structure reveals that the coupling of Cu-Fe is antiferromagnetic, while those of Cu-Cu and Fe-Fe are ferromagnetic.

Magnetic and electronic properties of CaCu3Cr4O12 and CaCu3Cr2Sb2O12 by first-principles density functional calculation

The electronic and magnetic properties of CaCu3Cr4O12 and CaCu3Cr2Sb2O12 are investigated by the use of the full-potential linearized augumented plane wave (FPLAPW) method. The calculated results indicate that CaCu3- Cr4O12 is a ferrimagnetic and half-metallic compound, in good agreement with previous theoretical studies. CaCu3- Cr2Sb2O12 is a ferrimagnetic semiconductor with a small gap of 0.136 eV. In both compounds, because Cr4+ 3d (d(2)) and Cr3+ 3d (d(3)) orbitals are less than half filled, the coupling between Cr-Cu is antiferromagnetic, whereas that between Cu-Cu and Cr-Cr is ferromagnetic. The total net spin moment is 5.0 and 3.0 mu(B) for CaCu3Cr4O12 and CaCu3Cr2Sb2O12, respectively. In CaCu3Cr4O12, the 3d electrons of Cr4+ are delocalized, which strengthens the Cr-Cr ferromagnetic coupling. For CaCu3Cr2Sb2O12, the doping of nonmagnetic ion Sb5+ reduces the Cr-Cr ferromagnetic coupling, and the half-filled Cr3+ t(2g) (t(2g)(3)) makes the chromium 3d electrons localized. In addition, the ordering arrangement of the octahedral chromium and antimony ions also prevents the delocalization of electrons. Hence, CaCu3Cr2Sb2O12 shows insulating behavior, in agreement with the experimental observation.

Generating Representative ISP Technologies From First-Principles

Understanding and modeling the factors that underlie the growth and evolution of network topologies are basic questions that impact capacity planning, forecasting, and protocol research. Early topology generation work focused on generating network-wide connectivity maps, either at the AS-level or the router-level, typically with an eye towards reproducing abstract properties of observed topologies. But recently, advocates of an alternative "first-principles" approach question the feasibility of realizing representative topologies with simple generative models that do not explicitly incorporate real-world constraints, such as the relative costs of router configurations, into the model. Our work synthesizes these two lines by designing a topology generation mechanism that incorporates first-principles constraints. Our goal is more modest than that of constructing an Internet-wide topology: we aim to generate representative topologies for single ISPs. However, our methods also go well beyond previous work, as we annotate these topologies with representative capacity and latency information. Taking only demand for network services over a given region as input, we propose a natural cost model for building and interconnecting PoPs and formulate the resulting optimization problem faced by an ISP. We devise hill-climbing heuristics for this problem and demonstrate that the solutions we obtain are quantitatively similar to those in measured router-level ISP topologies, with respect to both topological properties and fault-tolerance.

First principles modelling of nucleation and growth during atomic layer deposition onto III-V substrates

Atomic layer deposition (ALD) is now used in semiconductor fabrication lines to deposit nanometre-thin oxide films, and has thus enabled the introduction of high-permittivity dielectrics into the CMOS gate stack. With interest increasing in transistors based on high mobility substrates, such as GaAs, we are investigating the surface treatments that may improve the interface characteristics. We focus on incubation periods of ALD processes on III-V substrates. We have applied first principles Density Functional Theory (DFT) to investigate detailed chemistry of these early stages of growth, specifically substrate and ALD precursor interaction. We have modelled the ‘clean-up’ effect by which organometallic precursors: trimethylaluminium (TMA) or hafnium and titanium amides clean arsenic oxides off the GaAs surface before ALD growth of dielectric commences and similar effect on Si3N4 substrate. Our simulations show that ‘clean-up’ of an oxide film strongly depends on precursor ligand, its affinity to the oxide and the redox character of the oxide. The predominant pathway for a metalloid oxide such as arsenic oxide is reduction, producing volatile molecules or gettering oxygen from less reducible oxides. An alternative pathway is non-redox ligand exchange, which allows non-reducible oxides (e.g. SiO2) to be cleaned-up. First principles study shows also that alkylamides are more susceptible to decomposition rather than migration on the oxide surface. This improved understanding of the chemical principles underlying ‘clean-up’ allows us to rationalize and predict which precursors will perform the reaction. The comparison is made between selection of metal chlorides, methyls and alkylamides precursors.

A microscopic study of structural and electronic properties of functionalized silicon surfaces based on first-principles

Surface modification of silicon with organic monolayers tethered to the surface by different linkers is an important process in realizing future (opto-)electronic devices. Understanding the role played by the nature of the linking group and the chain length on the adsorption structures and electronic properties of these assemblies is vital to advance this technology. This Thesis is a study of such properties and contributes in particular to a microscopic understanding of induced changes in the work function of experimentally studied functionalized silicon surfaces. Using first-principles density functional theory (DFT), at the first step, we provide predictions for chemical trends in the work function of hydrogenated silicon (111) surfaces modified with various terminations. For nonpolar terminating atomic species such as F, Cl, Br, and I, the change in the work function is directly proportional to the amount of charge transferred from the surface, thus relating to the difference in electronegativity of the adsorbate and silicon atoms. The change is a monotonic function of coverage in this case, and the work function increases with increasing electronegativity. Polar species such as −TeH, −SeH, −SH, −OH, −NH2, −CH3, and −BH2 do not follow this trend due to the interaction of their dipole with the induced electric field at the surface. In this case, the magnitude and sign of the surface dipole moment need to be considered in addition to the bond dipole to generally describe the change in work function. Compared to hydrogenated surfaces, there is slight increase in the work function of H:Si(111)-XH, where X = Te, Se, and S, whereas reduction is observed for surfaces covered with −OH, −CH3, and −NH2. Next, we study the hydrogen passivated Si(111) surface modified with alkyl chains of the general formula H:Si–(CH2)n–CH2 and H:Si–X–(CH2)n–CH3, where X = NH, O, S and n = (0, 1, 3, 5, 7, 9, 11), at half coverage. For (X)–Hexyl and (X)–Dodecyl functionalization, we also examined various coverages up to full monolayer grafting in order to validate the result of half covered surface and the linker effect on the coverage. We find that it is necessary to take into account the van der Waals interaction between the alkyl chains. The strongest binding is for the oxygen linker, followed by S, N, and C, irrespective of chain length. The result revealed that the sequence of the stability is independent of coverage; however, linkers other than carbon can shift the optimum coverage considerably and allow further packing density. For all linkers apart from sulfur, structural properties, in particular, surface-linker-chain angles, saturate to a single value once n > 3. For sulfur, we identify three regimes, namely, n = 0–3, n = 5–7, and n = 9–11, each with its own characteristic adsorption structures. Where possible, our computational results are shown to be consistent with the available experimental data and show how the fundamental structural properties of modified Si surfaces can be controlled by the choice of linking group and chain length. Later we continue by examining the work function tuning of H:Si(111) over a range of 1.73 eV through adsorption of alkyl monolayers with general formula -[Xhead-group]-(CnH2n)-[Xtail-group], X = O(H), S(H), NH(2). The work function is practically converged at 4 carbons (8 for oxygen), for head-group functionalization. For tail-group functionalization and with both head- and tail-groups, there is an odd-even effect in the behavior of the work function, with peak-to-peak amplitudes of up to 1.7 eV in the oscillations. This behavior is explained through the orientation of the terminal-group's dipole. The shift in the work function is largest for NH2-linked and smallest for SH-linked chains and is rationalized in terms of interface dipoles. Our study reveals that the choice of the head- and/or tail-groups effectively changes the impact of the alkyl chain length on the work function tuning using self-assembled monolayers and this is an important advance in utilizing hybrid functionalized Si surfaces. Bringing together the understanding gained from studying single type functionalization of H:Si(111) with different alkyl chains and bearing in mind how to utilize head-group, tail-group or both as well as monolayer coverage, in the final part of this Thesis we study functionalized H:Si(111) with binary SAMs. Aiming at enhancing work function adjustment together with SAM stability and coverage we choose a range of terminations and linker-chains denoted as –X–(Alkyl) with X = CH3, O(H), S(H), NH(2) and investigate the stability and work function of various binary components grafted onto H:Si(111) surface. Using binary functionalization with -[NH(2)/O(H)/S(H)]-[Hexyl/Dodecyl] we show that work function can be tuned within the interval of 3.65-4.94 eV and furthermore, enhance the SAM’s stability. Although direct Si-C grafted SAMs are less favourable compared to their counterparts with O, N or S linkage, regardless of the ratio, binary functionalized alkyl monolayers with X-alkyl (X = NH, O) is always more stable than single type alkyl functionalization with the same coverage. Our results indicate that it is possible to go beyond the optimum coverage of pure alkyl functionalized SAMs (50%) by adding a linker with the correct choice of the linker. This is very important since dense packed monolayers have fewer defects and deliver higher efficiency. Our results indicate that binary anchoring can modify the charge injection and therefore bond stability while preserving the interface electronic structure.

Catalytic Water Formation on Platinum: A First-Principles Study

The study of catalytic behavior begins with one seemingly simple process, namely the hydrogenation of O to H2O on platinum. Despite the apparent simplicity its mechanism has been much debated. We have used density functional theory with,gradient corrections to examine microscopic reaction pathways for several elementary steps implicated in this fundamental catalytic process. We find that H2O formation from chemisorbed O and H atoms is a highly activated process. The largest barrier along this route, with a value of similar to1 eV, is the addition of the first H to O to produce OH. Once formed, however, OH groups are easily hydrogenated to H2O with a barrier of similar to0.2 eV. Disproportionation reactions with 1:1 and 2:1 stoichiometries of H2O and O have been examined as alternative routes for OH formation. Both stoichiometries of reaction produce OH groups with barriers that are much lower than that associated with the O + H reaction. H2O, therefore, acts as an autocatalyst in the overall H O formation process. Disproportionation with a 2:1 stoichiometry is thermodynamically and kinetically favored over disproportionation with a l:I stoichiometry. This highlights an additional (promotional) role of the second H2O molecule in this process. In support of our previous suggestion that the key intermediate in the low-temperature H2O formation reaction is a mixed OH and H2O overlayer we find that then is a very large barrier for the dissociation of the second H2O molecule in the 2:1 disproportionation process. We suggest that the proposed intermediate is then hydrogenated to H2O through a very facile proton transfer mechanism.

Solvation Structure and Transport of Acidic Protons in Ionic Liquids: A First-principles Simulation Study

Ab initio simulations of a single molecule of HCl in liquid dimethyl imidazolium chloride [dmim][Cl] show that the acidic proton exists as a symmetric, linear ClHCl- species. Details of the solvation structure around this molecule are given. The proton-transfer process was investigated by applying a force along the antisymmetric stretch coordinate until the molecule broke. Changes in the free energy and local solvation structure during this process were investigated. In the reaction mechanism identified, a free chloride approaches the proton from the side. As the original ClHCl- distorts and the incoming chloride forms a new bond to the proton, one of the original chlorine atoms is expelled and a new linear molecule is formed.

Electronic structure of the nitrogen-vacancy center in diamond from first-principles theory

The nitrogen-vacancy (NV) center is a paramagnetic defect in diamond with applications as a qubit. Here, we investigate its electronic structure by using ab initio density functional theory for five different NV center models of two different cluster sizes. We describe the symmetry and energetics of the low-lying states and compare the optical frequencies obtained to experimental results. We compute the major transition of the negatively charged NV centers to within 25–100 meV accuracy and find that it is energetically favorable for substitutional nitrogens to donate an electron to NV0. The excited state of the major transition and the NV0 state with a neutral donor nitrogen are found to be close in energy.

Hydrogenation of S to H2S on Pt(111): A first-principles study

Density-functional theory has been used to investigate the chemisorption of S, SH, and H2S as well as the coadsorption of S and H and SH and H on Pt(111). In addition reaction pathways and energy profiles for the conversion of adsorbed S and H into gas-phase H2S have been determined. It has been found that S, SH, and H2S bind preferentially at face-centered-cubic (fcc), bridge, and top sites, respectively. Both the S+H and SH+H reactions have high barriers (similar to1 eV) and high exothermicities (similar to1 eV). This reveals that adsorbed H2S and SH are highly unstable adsorbates on Pt(111) and that adsorbed S (and H) is the most stable SHX (X=0,1,2) intermediate on Pt(111) (C) 2001 American Institute of Physics.