Estimation of the micrometeorological parameters using on-site instrumentation

Summary Semi-empirical formulae, which have been proposed to estimate the Monin-Obukhov lengthL, are used to derive equations predicting the surface roughness lengthz ₀ and the potential temperature θ₀ at heightz ₀, using routine meteorological measurements. The friction velocityu _* is obtained from the computed values ofL andz ₀.     

Dependence of the wind profile power law exponent on the Pasquill stability classes and height interval in a stably stratified surface boundary layer.

Summary Using the logarithmic wind profile under stable stratification, a classification scheme was obtained for the Monin-Obukhov stability length and for the wind profile power law exponent in terms of the surface roughness length and the PasquillD-G stability classes, anywhere in the surface layer.     

Stability range for a flat graphene sheet subjected to in-plane deformation

The effects of the elastic deformation on the mechanical and physical properties of graphene are a subject of intensive current studies. Nevertheless, the stability range for a flat graphene sheet subjected to in-plane deformation is still unknown. Here, this problem is solved by atomistic simulations. In the three-dimensional space corresponding to the ɛ _xx , ɛ _yy , and ɛ _xy components of the planar strain tensor, the surface bounding the stability range for a flat graphene sheet has been constructed disregarding the thermal vibrations and the effects of boundary conditions. For the points of this surface, force components T _x , T _y , and T _xy have been calculated. It is shown that graphene is structurally stable up to strains on the order of 0.3–0.4, but it is unstable with respect to the shear in the absence of stretching forces. In addition, graphene cannot preserve its flat shape under the effect of a compressive force since it has zero flexural stiffness.     

Nanosize Semiconductors for Photooxidation

Nanosized semiconductors (semiconductor clusters) have the potential to revolutionize the fields of photooxidation and photocatalysis through the combined effects of quantum confinement and their unique surface morphologies. Photocatalytic oxidation as applied to environmental remediation (i.e., detoxification of chemical wastes), green/sustainable chemistry, as well as alternative energy paths (i.e., splitting of H ₂ O to produce H ₂ ) has already experienced improvements in activity, efficiency, and stability through the use of semiconductor nanoclusters based on materials such as TiO ₂ , MoS ₂ , WS ₂ , MoSe ₂ , FeS ₂ , and SnO ₂ . Issues such as improved control of size and surface chemistry play an important role in the success of these semiconductor nanocatalysts. This review explores the effect of advances in the fields of nanoscience and photocatalysis for current and future applications.     

Equations for the description of wave scattering by multi-valued random surfaces

We consider a scattering theory for multi-valued rough surfaces which cannot be described by the conventional equation of the type z = ζ(x,y). Both Dirichlet and Neumann problems are analyzed. Starting with Green's theorem we obtain a representation of the scattered field, the surface integral equation, and the extinction theorem for such surfaces. In contrast to conventional theory, these equations contain three random functions x = x(u ₁,u ₂), y = y(u ₁,u ₂), and z = z(u ₁,u ₂), where u ₁ and u ₂ are the parameters describing the surface. We introduce two scattering amplitudes S _± for describing the scattered wave above and below the surface. The extinction theorem, if formulated in terms of S _?, allows us to determine S _? for an arbitrary multi-valued surface and after this it becomes possible to derive a simple integral equation for surface sources. Knowledge of the surface sources allows us to find S ₊ by integration.     

On the relationship between the gradient and the bulk Richardson number for the atmospheric surface layer

Summary Semi-empirical formulations which have been proposed to describe the wind and potential temperature profiles are used to derive relationships between the gradient Richardson number, Ri, the finite-difference layer Richardson number, Ri_b, the surface layer Richardson number, Ri_s, and the bulk Richardson number,B, through the atmospheric surface layer. The theoretical analysis for stable conditions indicates that Ri (z ₃)=Ri_b, wherez ₃=(z ₂−z ₁)/ln(z ₂/z ₁), andz ₂;z ₁=upper and lower levels at which temperature and wind speed are specified. It is also found that, during stable conditions, the wind profile power law exponent,p, is computed at the heightz ₃, instead of the widely used geometric mean height,z _m, between top (z ₂) and bottom (z ₁) of the layer considered.     

Ab initio study of the chemical states of water on Cr2O3(0 0 0 1): From the isolated molecule to saturation coverage

The reactivity of the (0 0 0 1)-Cr–Cr₂O₃ surface towards water was studied by means of periodic DFT + U. Several water coverages were studied, from 1.2H₂O/nm² to 14.1H₂O/nm², corresponding to ¼, 1, 2 and 3 water/Cr at the (0 0 0 1)-Cr₂O₃ surface, respectively. With increasing coverage, water gradually completes the coordination sphere of the surface Cr atoms from 3 (dry surface) to 4 (1.2 and 4.7H₂O/nm²), 5 (9.4H₂O/nm²) and 6 (14.1H₂O/nm²). For all studied coverages, water replaces an O atom from the missing above plane. At coverages 1.2 and 4.7H₂O/nm², the Cr–O_s (surface oxygen) acid–base character and bond directionality govern the water adsorption. The adsorption is molecular at the lowest coverage. At 4.7H₂O/nm², molecular and dissociative states are isoenergetic. The activation energy barrier between the two states being as low as 12 kJ/mol, allowing protons exchanges between the OH groups, as evidenced by ab inito molecular dynamics at room temperature. At coverages of 9.4 and 14.1H₂O/nm², 1D- (respectively, 2D-) water networks are formed. The resulting surface terminations are –Cr(OH)₂ and –Cr(OH)₃– like, respectively. The increased stability of those terminations as compared to the previous ones are due to the stabilization of the adsorbed phase through a H-bond network and to the increase in the Cr coordination number, stabilizing the Cr (t_2g) orbitals in the valence band. An atomistic thermodynamic approach allows us to specify the temperature and water pressure domains of prevalence for each surface termination. It is found that the –Cr(OH)₃-like, –Cr(OH)₂ and anhydrous surfaces may be stabilized depending on (T, P) conditions. Calculated energies of adsorption and OH frequencies are in good agreement with published experimental data and support the full hydroxylation model, where the Cr achieves a 6-fold coordination, at saturation.     

Characteristics of the Surface-Intrinsic Josephson Junction

During the fabrication of intrinsic Josephson junctions (IJJs) with Bi₂Sr₂CaCu₂O_8+δ (BSCCO) single crystals, the superconductivity of the surface Cu-O layer is degraded because of a deposited metal film on top of the stack. Thus, the characteristics of the surface junction consisting of the surface Cu-O double layers remarkably differ from those of the junctions deep in the stack, which will be referred to as ordinary IJJs. The electrical transport characteristics of the surface junction, such as I-V, I _c′-T, and R-T, show that the critical temperature T _c′ of the surface junction is always lower than that of ordinary IJJs, and that the change of its critical current I _c′ with temperature is different from that of ordinary IIJs. Furthermore, by shunting the surface junction resistively, we are able to observe the AC Josephson effect at 3-mm waveband. Translated from Chinese Journal of Low Temperature Physics, 2005, 27(2) (in Chinese)     

The effect of Bi content on the thermal stability and crystallization of Se–Te chalcogenide glass

Glass formation and devitrification of intermediate alloys in the Se–Te–Bi system were studied by differential scanning calorimetry. A comparison of various simple quantitative methods to assess the level of stability of the glassy materials in the above-mentioned system is presented. All of these methods are based on characteristic temperatures, such as the glass transition temperature, T _g, the onset temperature of crystallization, T _in, the temperature corresponding to the maximum crystallization rate, T _p, or the melting temperature, T _m. In this work, a kinetic parameter, K _r(T), is added to the stability criteria. The thermal stability of several compositions of Se–Te–Bi was evaluated experimentally and correlated with the activation energies of crystallization by this kinetic criterion and compared with those evaluated by other criteria. All the results confirm that the thermal stability decreases with increasing Bi content in this glassy system. The crystallization results are analysed and the activation energy and mechanism of crystallization characterized.     

Kinetics of glass transition and thermal stability of?Se58Ge42?xPbx?(9≤x≤20) glasses

Se₅₈Ge_42−x Pb _x (9≤x≤20) glasses have been prepared using conventional melt quenching technique. Differential Scanning Calorimetric (DSC) measurements show single glass transition and double crystallization, which indicate the occurrence of phase separation in the samples. The phases present in the samples were identified using XRD. The kinetics of the glass transition has been studied in terms of the variation of glass transition temperature with composition and heating rate. In addition to this, activation energy of the glass transition (E _t ) has also been evaluated and its composition dependence is also investigated. The thermal stability of these glasses has been investigated using various stability criteria: Deiztal first glass criterion, ΔT, Saad and Poulain weighted thermal stability, H′ and the S-parameter. The values of these parameters were obtained using various characteristic temperatures such as the glass transition temperature, T _g , the onset temperature of crystallization, T _c , and the peak crystallization temperature, T _p . The values of stability parameters show that the phase corresponding to second crystallization is more stable than the phase corresponding to first one. The stability in terms of the lead (Pb) content has been determined considering the values of stability parameters of the phase corresponding to second peak. It was found that the stability increases with the lead content.     

Study of the Thermal Decomposition Behavior of Poly(vinyl alcohol) with NaHSO4

The thermal decomposition behavior of poly(vinyl alcohol) (PVA) with NaHSO₄ at 280～290°C as well as the optical characteristics and the thermal stability of the resulting thermally decomposed PVA were investigated by means of UV-Vis spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The results suggest that (1) the elimination reactions of side groups in PVA with NaHSO₄ can occur under our conditions resulting in formation of carbon–carbon double and triple bonds; (2) most of the carbon–carbon double bonds were conjugated; (3) the PVA thermally treated with NaHSO₄ could absorb light in the region of 190～600 nm; (4) the thermal stability of the resulting PVA was better than that of PVA without thermal treatment; and (5) compared with the thermal reaction of PVA without NaHSO₄, the addition of NaHSO₄ can promote the thermal elimination of side groups of PVA.     

The Stability of Several Triply Periodic Surfaces

The stability of six triply periodic surfaces of constant mean curvature (CMC) is investigated. The relative energy and curvature values of the surfaces comprising the P (Pm3¯m), I-WP (Im3¯m), and G (I4₁32) families are numerically calculated with K. Brakke's Surface Evolver. Regions where the I-WP surface can exist metastable to a complementary I-WP surface are found. This type of metastability is also found in the F-RD surface. Bifurcation points marking the stability limits of the P, I-WP, and G families are also calculated with Evolver. Modes of instability which may occur in the six CMC families are classified. Bifurcations in the P, G, I-WP, C(P), D, and F-RD families are attributed to fundamental instabilities. Lattices of spheres (LOS) are possible extremal surfaces at the bifurcations. It is determined that both the CMC surfaces and the LOS configurations are unstable to coarsening. Because the variation in curvature is lowest for the G family, it is the most robust of the six families to coarsening when the surfaces are otherwise equivalent.     

Thermal stability and crystallization kinetics of Ge–Se–Cd glasses

The effect is reported of varying cadmium concentration on the glass transition, thermal stability and crystallization kinetics of Ge₂₀Se_{80? x} Cd _x (x = 2.5, 5, 7.5 and 10 at. %) glasses. Differential scanning calorimetry results under non-isothermal conditions for the studied glasses are reported and discussed. The values of the glass transition temperature (T_g ) and the peak temperature of crystallization (T_p ) were found to be dependent on heating rate and Cd content. From the heating rate dependence of T_g and T_p , the values of the activation energy for glass transition (E_g ) and the activation energy for crystallization (E_c ) were evaluated and their composition dependence discussed. The thermal stability of the glasses was evaluated using various thermal stability criteria such as ΔT, H_g and S. The stability calculations emphasize that the thermal stability decreases with increasing Cd content.     

Quantum chemical studies on (ZnO)n/(NiO)n heterostructured nanoclusters

The structural stability and electronic properties of (ZnO)_n, (NiO)_n, (ZnO)_n/(NiO)_n for n = (1 to 4) and 3D structures were studied using density functional theory. The geometrical optimisation of clusters implies that when the atoms in the cluster increase it leads to an increase in its stability. The stability drastically increases for the heterostructure of (ZnO)_n/(NiO)_n. The dipole moment of the clusters depends on the geometry of the cluster and it is found to be minimum for heterostructures representing more neutralised clusters. HOMO-LUMO energies, ionisation potential, electron affinity, chemical hardness, binding energies and vibrational analysis of different clusters are calculated and reported. The adsorption of CO on the different sites of nanoclusters are studied and discussed.     

Mechanical and electronic properties of endofullerene Ne@C60 studied via structure distortions

Elastic, strength, electronic properties and vibrational spectra of Ne@C₆₀ (I _h) in its ground electronic state (X ¹A_g) were investigated with density functional theory at B3PW91/6-31G level via structure distortions. The elastic properties were obtained from the potential energy curves (PECs) in all of the five independent distortional directions of the molecule with symmetries of 1. D _5d, 2. D _3d, 3. D _2h, 4. C _2h(1) and 5. C _2h(2). PECs were examined where the structure of Ne@C₆₀ was destroyed. The necessary energies to destroy the structure were thus obtained, which illuminated the stability of Ne@C₆₀. PECs were found to be anisotropic and were accurately fitted to polynomials. Elongations in the direction of D _5d and compression in D _2h encountered potential energy surface cross-linkages, which might be considered as a single electron pump for further application in the design of single electron devices. Time-dependent B3PW91/6-31G analysis predicted significant electronic spectra changes associated with structure distortions. Similarities and differences of the properties were compared with those in C₆₀ and He@C₆₀.     

Role of anisotropy of the coupling constant in a superconductor model with singularities near the Fermi surface

The role of anisotropy of the coupling constant in the influence of nonmagnetic impurities on the behavior of the superconducting transition temperature T _c is investigated in the high-temperature superconductor (HTSC) model, where high values of T _c result from an increase in the density of states near the Fermi surface. It is shown that this model is more sensitive to impurities than the BCS model; Anderson compensation does not occur in the HTSC model, even for identical distributions of the densities of states in the superconducting and impurity channels, and the impurity contributions are no longer linear with respect to the impurity concentration in the vicinity of T _c. Anisotropy of the superconducting gap Δ and the possibility of its disappearance at certain points on the Fermi surface due to various types of pairing are manifested in the stability of the superconducting phase against the influence of impurities. Fiz. Tverd. Tela (St. Petersburg) 39, 1940–1942 (November 1997)     

Substituent effects on the conformational stability of allyl fluorides

By the B3P86/6‐311G(3d,2p) method, remote substituent effects on trans‐YCH?CHCH₂F were investigated by examining their conformational stabilities, molecular geometries, and stereoelectronic interactions in this paper. The cis conformer is favored for Y?H, Cl, Me, Vinyl, CF₃, CN, CHO, and NO₂, whereas the gauche is favored for Y?OMe, OH. A correlation of ΔH with the substituent constants σ⁺(Y) shows that the increasing electron‐withdrawing ability of the substituent Y increases the relative stability of the cis conformer. It was found that the substituent effect on the molecule stabilization energies (relative to CH₂?CHCH₂F) is more significant in the gauche conformers than in the cis conformers. In agreement, molecular structures of the gauche conformers were also observed to vary more significantly with the substitution than those of the cis conformers. By the second‐order perturbation energy (E(2)) in NBO analysis, it was found that the total C₂–C₃ vicinal hyperconjugation is determinant in the enthalpy difference and consequently controls the conformational stability. Further analysis shows that the substituent effect on the C₂–C₃ vicinal hyperconjugations is much higher in the gauche conformers than in the cis conformers. The highly sensitive π_C?C→σ*_{C? F} interaction to the substitution in the gauche conformers, is the leading factor in variation of molecular stability and geometry. Copyright © 2010 John Wiley & Sons, Ltd.     

Odd-even effect of the number of free valence electrons on the electronic structure properties of gold-thiolate clusters

ABSTRACT

It is essential to understand the intrinsic stability of the gold-thiolate clusters, which present extensive potential applications in many fields such as the catalysis, biomedicines and molecular machines. The electronic structures and aromaticity indexes of a series of Au_m(SH)_n (m, n?=?5–12) were comprehensively investigated through energetic, vibrational, magnetic, and electronic density properties, which are highly sensitive to the size and topological structure of the cluster. Generally, computational results of energy gap between the frontier molecular orbitals, normalized atomization energy (NAE), and electron localization function (ELF)-σ values exhibit the odd-even effect, in which clusters with the even number of free valence electrons, being reflected by the value of (m–n), possess relatively higher stability than the odd one. However, it is difficult to describe the stability of cluster with the sophisticated three-dimensional structure through one single aromaticity index such as the nucleus-independent chemical shift (NICS) value. Principal component analysis and clustering analysis of the calculation results of Au_m(SR)_n clusters suggest that the value of (m–n) and the Au₄ unit are important for predicting the stability of the Au clusters.     

Electronic structure of FeSi<Subscript>2</Subscript>

The electronic structure of volume and film iron disilicides with crystal structure of the type of α leboit and fluorite was calculated using the linearized augmented plane-wave formalism. Joint and local partial densities of electronic states, x-ray emission spectra in different series of all inequivalent atoms of these phases, and photoelectron spectra for different excitation energies were obtained. γ-FeSi₂ was found to be, unlike α-FeSi₂, an unstable phase in both the volume and film realizations. X-ray L _2,3 emission spectra of silicon in the iron group disilicides NiSi₂, CoSi₂, and FeSi₂ were compared. NiSi₂, CoSi₂, and α-FeSi₂ exhibit transformation of the maximum in the near-Fermi region of the Si L _2,3 spectra as one crosses over from a bulk to a film sample. This transformation is closely connected with phase stability and may serve as a criterion of thermodynamic stability of the iron-group transition-metal disilicides.     

Enhanced rear‐side reflection and firing‐stable surface passivation of silicon solar cells with capping polymer films

Low refractive index polymer materials have been investigated with a view to form the back surface mirror of advanced silicon solar cells. SiO_x:H or AlO_y SiO_x:H polymer films were spun on top of an ultra‐thin (<10 nm) atomic‐layer‐deposited (ALD) Al₂O₃ layer, itself deposited on low‐resistivity (1 Ω cm) p‐type crystalline silicon wafers. These double‐layer stacks were compared to both ALD Al₂O₃ single layers and ALD Al₂O₃/plasma‐enhanced chemical vapour deposited (PECVD) SiN_x stacks, in terms of surface passivation, firing stability and rear‐side reflection. Very low surface recombination velocity (SRV) values approaching 3 cm/s were achieved with ALD Al₂O₃ layers in the 4–8 nm range. Whilst the surface passivation of the single ALD Al₂O₃ layer is maintained after a standard firing step typical of screen printing metallisation, a harsher firing regime revealed an enhanced thermal stability of the ALD Al₂O₃/SiO_x:H and ALD Al₂O₃/AlO_y SiO_x:H stacks. Using simple two‐dimensional optical modelling of rear‐side reflection it is shown that the low refractive index exhibited by SiO_x:H and AlO_y SiO_x:H results in superior optical performance as compared to PECVD SiN_x, with gains in photogenerated current of ～0.125 mA/cm² at a capping thickness of 100 nm. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)