On the importance of long range summation of oscillatory interactions in Monte Carlo modeling

Kinetic and standard Monte Carlo (kMC and sMC) simulation of the system, where a pair-interaction energy is an oscillatory function of interatomic distance, requires a very careful selection of a cutoff radius r_cut of the pair-interactions. As an example, the homoepitaxy of Cu on Cu(1 1 1) is investigated. The surface-state mediated interaction between the Cu adatoms has a very long range and oscillates between attraction and repulsion as a function of the adatom-adatom distance. The simulations reveal that, at 15 K and 0.03 monolayer coverage, the Cu adatoms self-assemble into a dilute nanostructure with a weak local hexagonal order, where the average separation between adatoms equals 11.7 Å. The nanostructure consists of islands and chains of adatoms. The simulated structure of adlayer surprisingly strongly depends on the cutoff radius applied to the Monte Carlo model. The tendency to the dilute island formation strengthens and weakens with the same periodicity vs. r_cut as the pair-interaction energy vs. interatomic distance. The submonolayer morphology stabilizes when r_cut becomes longer than 50 Å.     

Oxygen adsorption and oxidation reactions on Au(2 1 1) surfaces: Exposures using O2 at high pressures and ozone (O3) in UHV

Nanosized gold particles supported on reducible metal oxides have been reported to show high catalytic activity toward CO oxidation at low temperature. This has generated great scientific and technological interest, and there have been many proposals to explain this unusual activity. One intriguing explanation that can be tested is that of Nørskov and coworkers [Catal. Lett. 64 (2000) 101] who suggested that the “unusually large catalytic activity of highly-dispersed Au particles may in part be due to high step densities on the small particles and/or strain effects due to the mismatch at the Au-support interface”. In particular, their calculations indicated that the Au(2 1 1) stepped surface would be much more reactive towards O₂ dissociative adsorption and CO adsorption than the Au(1 1 1) surface. We have now studied the adsorption of O₂ and O₃ (ozone) on an Au(2 1 1) stepped surface. We find that molecular oxygen (O₂) was not activated to dissociate and produce oxygen adatoms on the stepped Au(2 1 1) surface even under high-pressure (700 Torr) conditions with the sample at 300-450 K. Step sites do bind oxygen adatoms more tightly than do terrace sites, and this was probed by using temperature programmed desorption (TPD) of O₂ following ozone (O₃) exposures to produce oxygen adatoms up to a saturation coverage of θ_O = 0.90 ML. In the low-coverage regime (θ_O ? 0.15 ML), the O₂ TPD peak at 540 K, which does not shift with coverage, is attributed to oxygen adatoms that are bound at the steps on the Au(2 1 1) surface. At higher coverages, an additional lower temperature desorption peak that shifts from 515 to 530 K at saturation coverage is attributed to oxygen adsorbed on the (1 1 1) terrace sites of the Au(2 1 1) surface. Although the desorption kinetics are likely to be quite complex, a simple Redhead analysis gives an estimate of the desorption activation energy, E_d, for the step-adsorbed oxygen of 34 kcal/mol and that for oxygen at the terraces near saturation coverage of 33 kcal/mol, values that are similar to others reported on Au surfaces. Low Energy Electron Diffraction (LEED) indicates an oxygen-induced step doubling on the Au(2 1 1) surface at low-coverages (θ_O = 0.08-0.17 ML) and extensive disruption of the 2D ordering at the surface for saturation coverages of oxygen (θ_O ? 0.9 ML). Overall, our results indicate that unstrained step sites on Au(2 1 1) surfaces of dispersed Au nanoparticles do not account for the novel reactivity of supported Au catalysts for CO oxidation.     

Interaction of alkali metals with the Fe3O4(1 1 1) Surface

The adsorption and interaction of alkali metals (Li, Na, K, Rb and Cs) with the Fe_tet1-terminated Fe₃O₄(1 1 1) surface have been computed at the level of density functional theory. At low coverage, adsorption of alkali metals on site-1 (O_a-O_c-O_d) is energetically more favorable than on site-2 (O_a-O_c-O_d). Li has the strongest adsorption energy, followed by K, Rb, Cs and Na. The computed net charges show that the alkali metals can donate electrons to surface Fe and O atoms in the order of Li < Na < K ≈ Rb ≈ Cs. It is also noted that increasing the coverage does not significantly improve the promoting effect of alkali metals. In addition, alkali metals can move facilely on the Fe₃O₄(1 1 1) surface.     

Temperature dependent study of the crystal structure of NaCdZn2F7 pyrochlore

NaCdZn₂F₇ pyrochlore (Fd3¯m, Z=8), in which the Na and Cd cations are completely disordered, is shown to be structurally stable in the temperature range 100-643 K using X-ray diffraction and Raman scattering at atmospheric pressure. X-ray single-crystal measurements indicate that the (Na, Cd)F₈ cubes become more regular, while the ZnF₆ octahedra become more distorted in this structure upon cooling. The anomalous temperature-dependence of one of the Raman-active mode has been observed.     

Coverage temperature phase diagram of LEED spot and arced streak intensities for Li on Cu(0 0 1) surface using lattice gas model

It has been established that the arced streaks connecting four spots observed in LEED for a Li system adsorbed on a Cu(0 0 1) surface originate from the Bragg reflection from parallel adatomic lines on a c(2 × 2) lattice site. For example, one streak at about k_y = π/a originates from the parallel atomic lines including two atoms separated at a distance of d_y = 2a, which is the second-neighbor distance in a c(2 × 2) lattice.The c(2 × 2) structure sites consist of two sublattices with y = 2na and y = (2n + 1)a. Here, the difference in the number of adatoms on the two sublattices is the cause of the intensity of the midpoint of the streak, where the differences depend on the coverage of adatoms, Θ.In this study, using a lattice gas model on the substrate lattice with Monte Carlo simulation, we obtain the coverage and temperature dependence of intensities of the spots for the c(2 × 2) structure and the streaks.We found that the intensity of the streaks increase and decrease within the coverage range 0 < Θ < 0.5. That of the spots increases monotonically in this coverage range. These theoretical findings are similar to the experimental results.On the other hand, as temperature is increased, the intensity of the streaks increases and becomes saturated. We found a similar phenomenon using analytical calculation by statistical mechanics. In addition, the intensity of the spots decreased with the second-order transition.     

Anomalous adsorption of Cs on Pt(1 1 1)

The adsorption of Cs on Pt(1 1 1) surfaces and its reactivity toward oxygen and iodine for coverages θ_Cs?0.15 is reported. These surfaces show unusual “anomalous” behavior compared to higher coverage surfaces. Similar behavior of K on Pt(1 1 1) was previously suggested to involve incorporation of K into the Pt lattice. Despite the larger size of Cs, similar behavior is reported here. Anomalous adsorption is found for coverages lower than 0.15 ML, at which point there is a change in the slope of the work function. Thermal Desorption Spectroscopy (TDS) shows a high-temperature Cs peak at 1135 K, which involves desorption of Cs⁺ from the surface.The anomalous Cs surfaces and their coadsorption with oxygen and iodine are characterized by Auger Electron Spectroscopy (AES), TDS and Low Electron Energy Diffraction (LEED). Iodine adsorption to saturation on Pt(1 1 1)(anom)-Cs give rise to a sharp LEED pattern and a distinctive work function increase. Adsorbed iodine interacts strongly with the Cs and weakens the Cs-Pt bond, leading to desorption of Cs_xI_y clusters at 560 K. Anomalous Cs increases the oxygen coverage over the coverage of 0.25 ML found on clean Pt. However, the Cs-Pt bond is not significantly affected by coadsorbed oxygen, and when oxygen is desorbed the anomalous cesium remains on the surface.     

An ab initio-based approach to adsorption-desorption behavior of Si adatoms on GaAs(1 1 1)A-(2 × 2) surfaces

The adsorption-desorption behavior of Si adatoms on GaAs(1 1 1)A-(2 × 2) surfaces is investigated using our ab initio-based approach, in which adsorption and desorption behavior of Si adatoms is described by comparing the calculated desorption energy obtained by total-energy electronic-structure calculations with the chemical potential estimated by quantum statistical mechanics. We find that the Si adsorption at the Ga-vacancy site on the (2 × 2) surfaces with As adatoms occurs less than 1140-1590 K while the adsorption without As adatom does less than 630-900 K. The change in adsorption temperature of Si adatoms by As adatoms is due to self-surfactant effects of As adatoms: the promotion of the Si adsorption triggered by As adatoms is found to be interpreted in terms of the band-energy stabilization. Furthermore, the stable temperature range for Si adsorbed surfaces with As adatoms agrees with the experimental results. The obtained results provide a firm theoretical framework to clarify n-type doping processes during GaAs epitaxial growth.     

Electron stimulated desorption of cesium atoms from germanium-covered tungsten

The electron stimulated desorption (ESD) yield and energy distributions for Cs atoms from cesium layers adsorbed on germanium-covered tungsten have been measured for different Ge film thicknesses, 0.25-4.75 ML (monolayer), as a function of electron energy and cesium coverage Θ. The measurements have been carried out using a time-of-flight method and surface ionization detector. In the majority of measurements Cs is adsorbed at 300 K. The appearance threshold for Cs atoms is about 30 eV, which correlates well with the Ge 3d ionization energy. As the electron energy increases the Cs atom ESD yield passes through a wide maximum at an electron energy of about 120 eV. In the Ge film thickness range from 0.5 to 2 ML, resonant Cs atom yield peaks are observed at electron energies of 50 and 80 eV that can be associated with W 5p and W 5s level excitations. As the cesium coverage increases the Cs atom yield passes through a smooth maximum at 1 ML coverage. The Cs atom ESD energy distributions are bell-shaped; they shift toward higher energies with increasing cesium coverage for thin germanium films and shift toward lower energies with increasing cesium coverage for thick germanium films. The energy distributions for ESD of Cs from a 1 ML Ge film exhibit a strong temperature dependence; at T = 160 K they consist of two bell-shaped curves: a narrow peak with a maximum at a kinetic energy of 0.35 eV and a wider peak with a maximum at a kinetic energy of 0.5 eV. The former is associated with W level excitations and the latter with a Ge 3d level excitation. These results can be interpreted in terms of the Auger stimulated desorption model.     

X-ray diffraction, Cs and H NMR and thermal studies of CdZrCs1.5(H3O)0.5(C2O4)4·xH2O displaying Cs and water dynamic behavior

A novel mixed cadmium zirconium cesium oxalate with an open architecture has been synthesized from precipitation methods at room pressure. It crystallizes with an hexagonal symmetry, space group P3₁12 (no. 151), a=9.105(5) Å, c=23.656(5) Å, V=1698(1) Å³ and Z=3. The structure displays a [CdZr(C₂O₄)₄]²⁻ helicoidal framework built from CdO₈ and ZrO₈ square-based antiprisms connected through bichelating oxalates, which generates channels along different directions. Cesium cations, hydronium ions and water molecules are located inside the voids of the anionic framework. They exhibit a dynamic disorder which has been further investigated by ¹H and ¹³³Cs solid-state NMR. Moreover a phase transition depending both upon ambient temperature and water vapor pressure was evidenced for the title compound. The thermal decomposition has been studied in situ by temperature-dependent X-ray diffraction and thermogravimetry. The final product is a mixture of cadmium oxide, zirconium oxide and cesium carbonate.     

The ac transport and giant magnetoimpedance for sol–gel La0.67Ca0.33MnO3

In the present work, the temperature dependences of ac transport and magnetoimpedance for sol–gel La_0.67Ca_0.33MnO₃ manganite are investigated at various frequencies. The ac resistance R with absence of field shows a peak around the metal–insulator transition temperature T_MI for the dc case. A low magnetic field can shift the metal–insulator transition temperature more easily at high frequency than at low frequency. The valley phenomenon is observed in the temperature dependence of reactance X at 2 and 4 MHz, showing the effects of phase separation or grain boundaries. At 30 MHz, the peak of X appears instead of the valley, since the contribution of insulator capacitance term drops greatly and the inductance of metal dominates the X term with an increase of ac frequency in the sample. At 2 and 4 MHz, La_0.67Ca_0.33MnO₃ sol–gel manganite under H=1 kOe shows negative ac magnetoresistance ΔR/R₀, magnetoreactance ΔX/X₀ and magnetoimpedance ΔZ/Z₀ below 275 K, but positive ac ΔR/R₀, ΔX/X₀ and ΔZ/Z₀ near room temperature much higher than the Curie temperature. The peak temperature of R/R₀ moves to low temperature with an increase of the ac frequency from 2 to 4 MHz. At f=30 MHz, the absolute value of negative ac ΔR/R₀ increases monotonically with a decrease of temperature for 175 K<T<275 K, whereas the ΔX/X₀ is positive below 245 K but negative above 245 K. The ΔZ/Z₀ under H=1 kOe is positive below 238 K but negative above 238 K. Such a positive ΔZ/Z₀ is due to an increase of permeability induced by field. With an increase of field, the impedance Z experiences a peak, which is connected with the effect of transverse magnetic anisotropy.     

Metamagnetic transition and magnetocaloric effect in charge-ordered Pr0.68Ca0.32−xSrxMnO3 (x=0, 0.1, 0.18, 0.26 and 0.32) compounds

In this study, magnetic and magnetocaloric properties of Pr_0.68Ca_0.32−xSr_xMnO₃ (x=0, 0.1, 0.18, 0.26 and 0.32) compounds were investigated. X-ray results indicated that all the samples have a single phase of orthorhombic symmetry. The orthorhombic unit cell parameters increase with the increase in Sr content. Large negative magnetic entropy changes (−26.2 J/kg K at 38 K and 5 T for x=0 and −6.5 J/kg K at 83 K and 6 T for x=0.1) were attributed to ultrasharp metamagnetic transitions. The peak value of ΔS_m decreased from −4.1 J/kg K for x=0.18 sample to −2.4 J/kg K for x=0.32 at 1 T magnetic field.     

Bose-Einstein solitons in time-dependent linear potential

In this paper, Bose-Einstein soliton solutions of the nonlinear Schrödinger equation with time-dependent linear potential are considered. Based on the F-expansion method, we present a number of Jacobian elliptic function solutions. Particular cases of these solutions, where the elliptic function modulus equals 1 and 0, are various localized solutions and trigonometric functions, respectively. Specially, for V_ext = ZF(T) = Z[mg + Hcos (ω₁T)], we discussed the Bose-Einstein condensate trapped in the coupling external field with considering the effect of gravity; for F(T) = constant, it describes the wave (Langmuir or electromagnetic) in a linearly inhomogeneous plasma with cubic nonlinearly.     

Structural and magnetic properties of Zn1−xCoxO (0<x⩽0.30) nanoparticles

We present a systematic investigation on the structural and magnetic properties of Zn_1−xCo_xO nanoparticles synthesized by an auto-combustion method. The single-phase Zn_1−xCo_xO crystallize in the wurtzite-type structure with a homogeneity range as large as x≈0.30, which enables the observation of some anomalies. The lattice parameter a and the unit cell volume V increase with the Co content, and anomalies are discernable around x=0.15 on the a−x and V−x curves. The magnetization data show no evidence of ferromagnetic (FM) ordering in our samples down to T=5 K, and the magnetization at 5 K and 5 T exhibits a maximum around x=0.125. Based on the detailed analysis of the magnetization data and the donor impurity band exchange model, the anomalies on composition dependence of both the lattice parameters and magnetization can be associated with an occurrence of cation percolation around the threshold x_p (≈1.5/Z=0.125 for three-dimensional lattice with coordination number Z=12). Within the framework of the donor impurity band exchange model, the absence of FM in the well-characterized Zn_1−xCo_xO can be attributed to insufficient donor electron concentration.     

A scanning tunneling microscopy study of PH3 adsorption on Si(1 1 1)-7 × 7 surfaces, P-segregation and thermal desorption

PH₃ adsorption on Si(1 1 1)-7 × 7 was studied after various exposures between 0.3 and 60 L at room temperature by means of scanning tunneling microscopy (STM). PH₃-, PH₂-, H-reacted, and unreacted adatoms can be identified by analyzing empty-state STM images at different sample biases. PH_x-reacted rest-atoms can be observed in empty-state STM images if neighboring adatoms are hydrogen terminated. Most of the PH₃ adsorbs dissociatively on the surface, generating H- and PH₂-adsorbed rest-atom and adatom sites. Dangling-bonds at rest-atom sites are more reactive than adatom sites and the faulted half of the 7 × 7 unit cell is more reactive than the unfaulted half. Center adatoms are overwhelmingly preferred over corner adatoms for PH₂ adsorption. The saturation P coverage is ∼0.18 ML. Annealing of PH₃-reacted 7 × 7 surfaces at 900 K generates disordered, partially P-covered surfaces, but dosing PH₃ at 900 K forms P/Si(1 1 1)- surfaces. Si deposition at 510 K leaves disordered clusters on the surface, which cannot be reordered by annealing up to 800 K. However, annealing above 900 K recreates P/Si(1 1 1)- surfaces. Surface morphologies formed by sequential rapid thermal annealing are also presented.     

A new quasi-one-dimensional molecular solid based on Ni(mnt)2 anion: Crystal structure and spin-gap transition

A new molecular solid, [1-(4′-bromo-2′-fluorobenzyl)-4-dimetylaminopyridinium]-bis(maleonitriledithiolato)nickel(III), (BrFBzPyN(CH₃)₂(Ni(mnt)₂)(1), has been prepared and characterized by elemental analyses, IR, ESI-MS spectra, single crystal X-ray diffraction and magnetic measurements. Compound 1 crystallizes in the orthorhombic space group Pnma, a=20.579(4) Å, b=7.078(1) Å, c=17.942(4) Å, α=β=γ=90°, V=2613.3(9) Å³, Z=4. The Ni(III) ions of 1 form a quasi-one-dimensional Zigzag magnetic chain within a Ni(mnt)₂⁻ column through Ni?S, S?S, Ni?Ni, or π?π interactions with an Ni?Ni distance of 4.227 Å. Magnetic susceptibility measurements in the temperature range 2-300 K show that 1 exhibits a spin-gap transition around 200 K, and antiferromagnetic interaction in the high-temperature phase (HT) and spin gap in the low-temperature phase (LT). The transition for 1 is second-order phase transition as determined by DSC analyses.     

Synthesis, structure and magnetic properties of the new double perovskite Ca2CrSbO6

The title double perovskite has been synthesized by solid-state reaction in air. The crystal structure has been studied from powder X-ray diffraction data. Rietveld fits to the pattern show that this compound has a monoclinic symmetry [a=5.4932(3) Å, b=5.4081(3) Å, c=7.6901(5) Å, β=90.0022(1)°, at 300 K] defined in the space group P2₁/n, where the Cr and Sb cations are almost completely ordered in the B-sublattice of the perovskite structure. Magnetic susceptibility and magnetization measurements show that this compound behaves as a Curie-Weiss paramagnet at high temperatures with μ_eff=3.53(1) μ_B and θ_P=8 K, and exhibits a robust ferromagnetic component below the ordering temperature of T_C=13 K, with a saturation magnetization of 2.36 μ_B/f.u. at 5 K. To our knowledge, this is the first example of a ferromagnetic double perovskite containing a non-magnetic element, such as Sb, occupying one half of the B positions of the perovskite structure.     

Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

Method for measurements of second-order nonlinear optical coefficient based on Z-scan

The method for measuring second-order nonlinear optical coefficients based on well-known Z-scan is presented. The influence of linear absorption coefficients on normalized transmittance is discussed. Using this method, we obtained the second-order nonlinear coefficient d₃₁(5%MgO:LiNbO₃) = 4.5 × 10⁻¹² m/v at 1064 nm, which agrees well with theoretical calculations and previous well-known values.     

Formation of a cubic Sr2MnWO6 phase at elevated temperature; a neutron powder diffraction study

In a temperature dependent neutron powder diffraction (NPD) study we observed the high temperature cubic phase at 973 K in the polycrystalline double perovskite Sr₂MnWO₆. Rietveld analysis of the NPD data shows that the room temperature tetragonal phase exists up to 573 K (space group P4₂/n, a=8.0119 (4) Å, c=8.0141(8) Å). At 773 K, the primitive tetragonal symmetry change to body-centred tetragonal (space group I4/m, a=5.6935(5) Å, c=8.077(1) Å) and finally at 973 K it becomes face-centred cubic (space group Fm-3m, a=8.0864(8) Å). The changes in the structural symmetry are connected to the small distortion of the B-site octahedra, which are insensitive to the Differential Thermal Analysis (DTA) signal.     

Surface morphology of metal films deposited on mica at various temperatures observed by atomic force microscopy

Thin films of eight metals with a thickness of 150 nm were deposited on mica substrates by thermal evaporation at various temperatures in a high vacuum. The surface morphology of the metal films was observed by atomic force microscopy (AFM) and the images were characterized quantitatively by a roughness analysis and a bearing analysis (surface height analysis). The films of Au, Ag, Cu, and Al with the high melting points were prepared at homologous temperatures T/T_m = 0.22-0.32, 0.40, and 0.56. The films of In, Sn, Bi, and Pb with the low melting points were prepared at T/T_m = 0.55-0.70, where T and T_m are the absolute temperatures of the mica substrate and the melting point of the metal, respectively. The surface morphology of these metal films was studied based on a structure zone model. The film surfaces of Au, Ag, and Cu prepared at the low temperatures (T/T_m = 0.22-0.24) consist of small round grains with diameters of 30-60 nm and heights of 2-7 nm. The surface heights of these metal films distribute randomly around the surface height at 0 nm and the morphology is caused by self-shadowing during the deposition. The grain size becomes large due to surface diffusion of adatoms and the film surfaces have individual characteristic morphology and roughnesses as T increases. The surface of the Al film becomes very smooth as T increases and the atomically smooth surface is obtained at T/T_m = 0.56-0.67 (250-350 °C). On the other hand, the atomically smooth surface of the Au film is obtained at T/T_m = 0.56 (473 ± 3 °C). The films of In, Sn, Bi, and Pb prepared at T/T_m = 0.55-0.70 also show the individual characteristic surface morphology.