A comparative study of ethylene oxide and diethylene dioxide adsorption on silicon (0 0 1)

The adsorption of ethylene oxide (oxirane) and diethylene dioxide (1,4-dioxane) on the Si(0 0 1) surface was investigated using the first-principles pseudopotential method within a generalised gradient approximation to the density functional theory. Our results indicate that oxirane adsorption on the silicon surface probably occurs via C-C bond. This interaction induces the breaking of the C-C bond and the formation of a Si-C-O-C-Si ring. The 1,4-dioxane interaction with the silicon (2 × 2) surface, on the other hand, results in the decomposition of the considered molecule in different radicals, depending on the original adsorbed structure. In order to disregard the possible influence of the slab considered, we suggest that high order reconstruction surfaces, i.e. (4 × 2) or (4 × 4), should be investigated.     

Correlations between magnetic properties and bond formation in Rh-MgO(0 0 1)

We present the results of first principles calculations for the magnetism of Rh adlayers on MgO(0 0 1), at three different adsorption sites and three different coverages, corresponding to 1, 1/2 and 1/8 monolayers. Finite magnetization is found in all cases except that of one Rh monolayer above the oxygen site, which is also the most stable. We examine how the magnetization changes as a function of the Rh-surface distance and relate this to changes in the real-space charge density and in the density of states (DOS) as the Rh adlayer interacts with the surface. We find that increasing either the Rh-Rh interaction strength or the Rh-surface interaction strength leads to reduced magnetization, while increasing the former drives a crossover from localized (atomic) to itinerant magnetism. Neither the magnetic transition itself, nor the localized-to-itinerant magnetism crossover, is found to be directly related to the formation of Rh-surface bonds. From a practical point of view, we predict that magnetism in the Rh-MgO(0 0 1) system is most likely to be found experimentally at reduced coverages and at low temperatures.     

Effect of hydrogenation on B/Si(0 0 1)-(1 × 2)

Ab initio calculations, based on pseudopotentials and density functional theory, have been performed to investigate the effect of hydrogenation on the atomic geometries and the energetics of substitutional boron on the generic Si(0 0 1)-(1 × 2) surface. For a single B atom substitution corresponding to 0.5 ML coverage, we have considered two different sites: (i) the mixed Si-B dimer structure and (ii) boron substituting for the second-layer Si to form Si-B back-bond structure, which is energetically more favorable than the mixed Si-B dimer by 0.1 eV/dimer. However, when both of these cases are passivated by hydrogen atoms, the situation is reversed and the Si-B back-bond case becomes 0.1 eV/dimer higher in energy than the mixed Si-B dimer case. For the B incorporation corresponding to 1 ML coverage, among the substitutional cases, 100% interdiffusion into the third layer of Si and 50% interdiffusion into the second layer of Si are energetically similar and more favorable than the other cases that are considered. However, when the surface is passivated with hydrogen, the B atoms energetically prefer to stay at the third layer of the Si substrate.     

Density functional study of α–β phase transition of polyvinylidene difluoride

We perform density functional calculations to investigate structural and dynamical properties of crystalline polyvinylidene difluoride (PVDF) associated with the transition from α to β phase. We examine the change of the conformational energy and the corresponding structure of each phase depending on the lattice parameters of the orthorhombic crystalline structure. From this information, we construct the path that connects the point where the α phase is most stable to the point where the β phase is most stable, and identify the sub‐ region in the lattice parameter space where α and β phases have the same energy. In this sub‐region, we locate the point which gives the lowest conformation energy for both α and β phases, and examine the behaviour of the lowest energy profile and corresponding change of intermediate structures as the conformation of the PVDF chain transforms from α phase to β phase. Finally we perform ab‐initio molecular dynamics simulations and analyse the characteristic dynamics associated with transition from α to β phase. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A DFT + U description of oxygen vacancies at the TiO2 rutile (1 1 0) surface

Experimental observations indicate that removing bridging oxygen atoms from the TiO₂ rutile (1 1 0) surface produces a localised state approximately 0.7 eV below the conduction band. The corresponding excess electron density is thought to localise on the pair of Ti atoms neighbouring the vacancy; formally giving two Ti³⁺ sites. We consider the electronic structure and geometry of the oxygen deficient TiO₂ rutile (1 1 0) surface using both gradient-corrected density functional theory (GGA DFT) and DFT corrected for on-site Coulomb interactions (GGA + U) to allow a direct comparison of the two methods. We show that GGA fails to predict the experimentally observed electronic structure, in agreement with previous uncorrected DFT calculations on this system. Introducing the +U term encourages localisation of the excess electronic charge, with the qualitative distribution depending on the value of U. For low values of U (?4.0 eV) the charge localises in the sub-surface layers occupied in the GGA solution at arbitrary Ti sites, whereas higher values of U (?4.2 eV) predict strong localisation with the excess electronic charge mainly on the two Ti atoms neighbouring the vacancy. The precise charge distribution for these larger U values is found to differ from that predicted by previous hybrid-DFT calculations.     

Magnetic Phase Transition Driven by Frustrated Interactions in a Longitudinal‐Field Ising Chain

The ground‐state magnetic phase transitions in a classical spin chain with long‐range interactions in a system of trapped ions are investigated. The tunable competing interactions, mediated by both longitudinal and transverse photon modes, lead to competition among different spins, due to which magnetic frustration occurs. Various ground‐state spin configurations are separated by multiple phase transitions when the strength and sign of these interactions are tuned continuously. The spin chains are highly degenerated because of the frustration, so there is some melting of several magnetic phases.     

A correlation between the structural and magnetic phase transitions for the mixed systems: KMn1-xNixF3 and KMn1-xCoxF3. II. Magnetic properties

Susceptibility measurements at temperatures from 55 K to 620 K are reported for the mixed crystals KMn_1-xCo_xF₃ where x 0.10. All the compounds show antiferromagnetism and a transition to a weak ferromagnetic phase below T _N . The observed phase transition AF—WF is very sensitive to the presence of admixtures, which changes not only the phase transition temperature, but also it's character. A strong correlation between the structural and magnetic phase transition is evident from our study.     

Optical anisotropy at the W(1 1 0) surface

We report ab initio calculations of the anisotropic dielectric function of tungsten (1 1 0) surface using the linear muffin-tin-orbital method. The calculated anisotropy in the optical spectrum, for polarization of light parallel to the surface, exhibits three dominant broad structures at 3.00, 4.01 and 5.34 eV successively positive, negative and then positive. The first peak is clearly assigned to p → d interband transitions in surface atomic sites whereas the two others have their origin in interband transitions in bulk like atoms. Our results, including the interlayer relaxation effect on the surface optical response, are compared to recent reflectance anisotropy measurements.     

Non-collinear magnetisation of V clusters supported on a Cu (1 1 1) surface: Theory

Magnetic properties and electronic structure of V clusters supported on a Cu (1 1 1) substrate, have been calculated from a first principles method. We observe in general non-collinear magnetic structures that are the result of antiferromagnetic interactions on a frustrated lattice. The values of the magnetic moments range from ∼0 to 2.7 μ_B/atom, depending on cluster geometry.     

Antiferromagnetic Ordering in TmCu2

Intermetallic compound TmCu₂ crystalizes in the orthorhombic structure, orders antiferromagnetically (AF) and exhibits four different AF phases below T _N = 6.5 K. In all these phases the Tm magnetic moment is parallel to the b-axis. The ground-state AF1 (T < 3.4 K) corresponds to the squared-up AF structure with propagation vector ₀₁ = (5/8, 0, 0) and magnetic unit cell 8a × b × c. Narrow phases AF2 and AF3 (3.3 K < T < 3.7 K and 3.6 K < T < 4.6 K) are 'spin-slip'-derivatives from the AF1 structure, yielding propagation vectors ₀₂ = (0.633, 0, 0.02) and ₀₃ = (0.618, 0, 0), respectively. The phase AF4 (4.4 K < T < T _N) is then incommensurate transversal spin-wave with the propagation ₀₄ = (0.64, 0, 0). The co-existence of AF phases indicates the first-order transitions between them.     

Bistability in a H-terminated Si(1 0 0)2 × 1 surface obtained by ab initio transport calculations

We have analyzed electron tunneling due to the electric field from a hydrogen-terminated Si(1 0 0)2 × 1 ultrathin film on a metal substrate by density functional transport calculations. We have obtained a hysteresis loop in the tunneling current, which comes from the existence of two electronic structures. Furthermore, we have clarified that, as a condition of bistable electron transport, a double-barrier potential structure is not necessarily required for zero field, because it can be induced by the electric field.     

Microscopic model of CO oxidation on Pt(1 1 1)

A new microscopic model, based on DFT/LDA modeling, is suggested for the Langmuir-Hinshelwood reaction of catalytic CO oxidation in coadsorbed O-CO layers on Pt(1 1 1). It has been found that only the oxygen atoms occupying threefold hollow sites of hcp type are chemically active. The potential barrier for the oxidation reaction significantly decreases due to changes in the adlayer oxygen states in the proximity to CO. The oxygen electronic density distribution is affected by approaching CO molecule which alters the oxygen position. Height of the barrier is estimated as 1.15 eV, which may be attributed to the upper limit of activation energy for the net reaction process.     

First-principles study of adsorption and diffusion on Ge/Si(0 0 1)-(2 × 8) and Ge/Si(1 0 5)-(1 × 2) surfaces

Using first-principles total-energy calculations, we have investigated the adsorption and diffusion of Si and Ge adatoms on Ge/Si(0 0 1)-(2 × 8) and Ge/Si(1 0 5)-(1 × 2) surfaces. The dimer vacancy lines on Ge/Si(0 0 1)-(2 × 8) and the alternate S_A and rebonded S_B steps on Ge/Si(1 0 5)-(1 × 2) are found to strongly influence the adatom kinetics. On Ge/Si(0 0 1)-(2 × 8) surface, the fast diffusion path is found to be along the dimer vacancy line (DVL), reversing the diffusion anisotropy on Si(0 0 1). Also, there exists a repulsion between the adatom and the DVL, which is expected to increase the adatom density and hence island nucleation rate in between the DVLs. On Ge/Si(1 0 5)-(1 × 2) surface, the overall diffusion barrier of Si(Ge) along direction is relative fast with a barrier of ∼0.83(0.61) eV, despite of the large surface undulation. This indicates that the adatoms can rapidly diffuse up and down the (1 0 5)-faceted Ge hut island. The diffusion is also almost isotropic along [0 1 0] and directions.     

Barrier Li Quantum Dots in Magnetic Fields

The methods for the few-body system are introduced to investigate the states of the barrier Li quantumdots (QDs) in an arbitrary strength of magnetic field. The configuration, which consists of a positive ion located on thez-axis at a distance d from the two-dimensional QD plane (the x-y plane) and three electrons in the dot plane boundby the positive ion, is called a barrier Li center. The system, which consists of three electrons in the dot plane bound bythe ion, is called a barrier Li QD. The dependence of energy of the state of the barrier Li QD on an external magneticfield B and the distance d is obtained. The angular momentum L of the ground states is found to jump not only withthe variation of B but also with d.     

Barrier Li Quantum Dots in Magnetic Fields

The methods for the few-body system are introduced to investigate the states of the barrier Li quantum dots (QDs) in an arbitrary strength of magnetic field. The configuration, which consists of a positive ion located on the z-axis at a distaneed from the two-dimensional QD plane (the x-y plane) and three electrons in the dot plane bound by the positive ion, is called a barrier Li center. The system, which consists of three electrons in the dot plane bound by the ion,is called a barrier Li QD. The dependence of energy of the state of the barrier Li QD on an external magnetic field B and the distance d is obtained. The angular momentum L of the ground states is found to jump not only with the variation orB but also with d.     

Ground-state properties of arsenic deposited on the Ge(0 0 1)(2 × 1) surface

We present results of ab initio calculations of structural, electronic and vibrational properties of the Ge(0 0 1) surface covered with a monolayer of arsenic. The fully occupied π_u bonding and π_g antibonding electronic states due to the As-As dimer formation are quite close in energy and their ordering is same as that found on the Si(0 0 1) surface. Using our calculated atomic and electronic structures, surface lattice dynamics was studied by employing a linear response approach based on density functional perturbation theory. A comparison of the phonon spectrum of the Ge(0 0 1)/As(2 × 1) surface with that of the clean Ge(0 0 1)(2 × 1) surface indicates the presence of several new characteristic phonon modes due to adsorption of As atoms.     

STM study of Si(1 1 3) 3 × 2-Ga surface

The Ga-adsorbed structure on Si(1 1 3) surface at low coverage has been studied by scanning tunneling microscopy (STM). The bright protrusion corresponding to the position of the dimer without the interstitial Si atom of the clean surface disappeared in the filled-state STM image after Ga adsorption, although the protrusion due to the Si adatom still remained. On the basis of the adatom-dimer-interstitial (ADI) model, this result indicates that the Ga atom is adsorbed interstitially at the center of another pentamer that does not have the interstitial Si atom. An ab initio calculation was performed and STM images were simulated.     

Adsorbate influence on the coercive field of ultrathin Co/Cu{1 1 0}

We report on experimental coercive field measurements for ultrathin films of Co on Cu{1 1 0}, revealing a complex dependence upon the surface coverage of oxygen and hydrogen adatoms. With reference to first-principles calculations, we rationalise this behaviour in terms of initial reaction with surface contaminants and/or adsorption at defects, followed by (in the case of oxygen) subsequent surface ordering and eventual formation of surface oxide.     

Improved growth and the spin reorientation transition of Ni on (√2×2√2)R45° reconstructed O/Cu(0 0 1)

Ni films between 1 and 20 monolayers (ML) thick are deposited at room temperature on clean and (√2×2√2)R45° reconstructed--via oxygen adsorption--Cu(0 0 1). A significant expansion of the out-of-plane Ni phase by about 5 ML is revealed by ferromagnetic resonance experiments. This shift of the spin reorientation transition is attributed to a huge change of about 90 μeV/atom in the surface anisotropy due to the presence of half a monolayer of oxygen atoms on the top of Ni. Furthermore, the growth of Ni on the preoxidized Cu surface is found to be closer to the layer-by-layer one as compared to the growth on the clean Cu(0 0 1) due to the presence of oxygen which acts as a surfactant.