Specific Features of the Local Structure and Transport Properties of ZrO2–Sc2O3–Y2O3 and ZrO2–Sc2O3–Yb2O3 Crystals

Optics and Spectroscopy - The specific features of the local structure of ZrO2–Sc2O3–Y2O3 and ZrO2–Sc2O3–Yb2O3 crystals are revealed by optical spectroscopy using the Eu3+...     

Photoconductive detector of circularly polarized radiation based on a MIS structure with a CoPt layer

Physics of the Solid State - A photoconductive detector of circularly polarized radiation based on the metal–insulator–semiconductor structure of CoPt/(Al2O3/SiO2/Al2O3)/InGaAs/GaAs is...     

Analytical representation of half-width for molecular ro-vibrational lines in the case of dipole–dipole and dipole–quadrupole interactions

The analytical formula for half-width of molecular ro-vibrational lines is obtained for the case of dipole–dipole and dipole–quadrupole interactions. This formula depends on the variable parameters, which have to be determined by fitting to experimental half-widths or to half-widths calculated by semi-classical methods. The application of the analytical formula to the H₂O–H₂O, NH₃–NH₃, DCl–HCl and CO–H₂O systems is discussed.     

Density functional study of uranyl （VI） amidoxime complexes

Uranyl (Ⅵ) amidoxime complexes are investigated using relativistic density functional theory. The equilibrium structures, bond orders, and Mulliken populations of the complexes have been systematically investigated under a generalized gradient approximation (GGA). Comparison of (acet) uranyl amidoxime complexes ([UO 2 (AO) n ] 2 n , 1≤ n ≤4) with available experimental data shows an excellent agreement. In addition, the U-O(1), U-O(3), C(1)-N(2), and C(3)-N(4) bond lengths of [UO 2 (CH 3 AO) 4 ] 2 are longer than experimental data by about 0.088, 0.05, 0.1, and 0.056 A. The angles of N(3)-O(3)-U, O(2)-N(1)-C(1), N(3)-C(3)-N(4), N(4)-C(3)-C(4), and C(4)-C(3)-N(3) are different from each other, which is due to existing interaction between oxygen in uranyl and hydrogen in amino group. This interaction is found to be intra-molecular hydrogen bond. Studies on the bond orders, Mulliken charges, and Mulliken populations demonstrate that uranyl oxo group functions as hydrogen-bond acceptors and H atoms in ligands act as hydrogen-bond donors forming hydrogen bonds within the complex.     

Computational study on structures,thermochemical properties,and bond energies of disulfide oxygen (S–S–O)‐bridged CH3SSOH and CH3SS(=O)H and radicals

Cleavage of disulfide bonds is a common method used in linking peptides to proteins in biochemical reactions. The structures, internal rotor potentials, bond energies, and thermochemical properties (Δ_fH°, S°, and Cp(T)) of the S–S bridge molecules CH₃SSOH and CH₃SS(=O)H and the radicals CH₃SS?=O and C?H₂SSOH that correspond to H‐atom loss are determined by computational chemistry. Structure and thermochemical parameters (S° and Cp(T)) are determined using density functional Becke, three‐parameter, Lee–Yang–Parr (B3LYP)/6‐31++G (d, p), B3LYP/6‐311++G (3df, 2p). The enthalpies of formation for stable species are calculated using the total energies at B3LYP/6‐31++G (d, p), B3LYP/6‐311++G (3df, 2p), and the higher level composite CBS–QB3 levels with work reactions that are close to isodesmic in most cases. The enthalpies of formation for CH₃SSOH, CH₃SS(=O)H are ?38.3 and ?16.6 kcal mol^?1, respectively, where the difference is in enthalpy RSO–H versus RS(=O)–H bonding. The C–H bond energy of CH₃SSOH is 99.2 kcal mol^?1, and the O–H bond energy is weaker at 76.9 kcal mol^?1. Cleavage of the weak O–H bond in CH₃SSOH results in an electron rearrangement upon loss of the CH₃SSO–H hydrogen atom; the radical rearranges to form the more stable CH₃SS· = O radical structure. Cleavage of the C–H bond in CH₃SS(=O)H results in an unstable [CH₂SS(=O)H]* intermediate, which decomposes exothermically to lower energy CH₂ = S + HSO. The CH₃SS(=O)–H bond energy is quite weak at 54.8 kcal mol^?1 with the H–C bond estimated at between 91 and 98 kcal mol^?1. Disulfide bond energies for CH₃S–SOH and CH3S–S(=O)H are low: 67.1 and 39.2 kcal mol^?1. Copyright © 2011 John Wiley & Sons, Ltd.     

First-principles study of the adhesive and mechanical properties of the O-terminated α-Al2O3(0001)/Cu(111) interfaces

Adhesive and mechanical properties of the O-terminated (O-rich) α-Al₂O₃(0001)/Cu(111) interface have been examined by the first-principles pseudopotential method. Strong Cu–O covalent and ionic interactions exist, such as Cu3d–O2p hybridization and substantial electron transfer from Cu to O, which result in larger adhesive energy, greater tensile strength and larger interfacial Young's moduli than the Al-terminated (stoichiometric) interface with electrostatic–image and Cu–Al hybridization interactions. Substantial effects of interfacial Cu–O coordination are also present. Changes in the interface electronic structure for cleavage have been examined. Cu–O interlayer potential curves have been analyzed using the universal binding energy relation and compared with Cu–Al and Cu–Cu curves, which is valuable for the development of effective interatomic potentials in large-scale simulations.     

Comparison for σ-hole and π-hole tetrel-bonded complexes involving cyanoacetaldehyde

Ab initio calculations have been performed for the complexes of cyanoacetaldehyde (CA) with TH₃F (T = C, Si, Ge and Sn) and F₂TO (T = C and Si). The σ-hole and π-hole tetrel-bonded complexes are formed for TH₃F and F₂TO, respectively. In general, three minima complexes (N, O–A and O–B) are obtained for each tetrel donor. Most complexes are stabilised by a primary tetrel bond and a secondary hydrogen bonding. TH₃F–N/F₂CO–N has greater stability than TH₃F–O/F₂CO–O, but a reverse result is found in the complexes of F₂SiO although they have comparative interaction energies. Charge transfer from the lone pair on the N/O atom of CA into the T–F σ^* antibonding orbital leads to the stabilisation of the TH₃F complexes. Accordingly, the T–F bond is extended and its stretch vibration displays a redshift. A breakdown of the individual forces involved attributes the stability of the complex mainly to electrostatic energy, with relatively large dispersion term in the CH₃F complexes and relatively large polarisation energy in the F₂SiO complexes.     

The adsorption and reaction of ethylene glycol and 1,2-propanediol on Pd(111): A TPD and HREELS study

The reactions of ethylene glycol and 1,2-propanediol have been studied on Pd(111) using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). Both molecules initially decompose through O–H activation, forming ethylenedioxy (–OCH₂CH₂O–) and 1,2-propanedioxy (–OCH₂CH(CH₃)O–) surface intermediates. For ethylene glycol, increases in thermal energy lead to dehydrogenation and formation of carbonyl species at both oxygen atoms. The resulting glyoxal (O═CHCH═O) either desorbs molecularly or reacts through one of two competing pathways. The favored pathway proceeds via C–C bond scission, dehydrogenation, and decarbonylation to form carbon monoxide and hydrogen. In a minor pathway, small amounts of glyoxal undergo C–O bond scission and recombination with surface hydrogen to form ethylene and water. The same reaction mechanism occurs for 1,2-propanediol after methyl elimination and formation of glyoxal. However, this is accompanied by a minor pathway involving a methylglyoxal (O=CHC(CH₃)=O) intermediate. The prevalence of the dehydrogenation/decarbonylation pathway in the current work is consistent with the high selectivity for C–C scission in the aqueous phase reforming of polyols on supported Pd catalysts.     

Theoretical investigation on the electronic structure,elastic properties,and intrinsic hardness of Si₂N₂O

According to the density functional theory we systematically study the electronic structure, the mechanical prop- erties and the intrinsic hardness of Si2N2O polymorphs using the first-principles method. The elastic constants of four Si2N2O structures are obtained using the stress-strain method. The mechanical moduli (bulk modulus, Young’s mod- ulus, and shear modulus) are evaluated using the Voigt-Reuss-Hill approach. It is found that the tetragonal Si2N2O exhibits a larger mechanical modulus than the other phases. Some empirical methods are used to calculate the Vickers hardnesses of the Si2N2O structures. We further estimate the Vickers hardnesses of the four Si2N2O crystal structures, suggesting all Si2N2O phases are not the superhard compounds. The results imply that the tetragonal Si2N2O is the hardest phase. The hardness of tetragonal Si2N2O is 31.52 GPa which is close to values of β-Si3N4 and γ-Si3N4.     

Electron density characteristics and charge transfer effect of hydrogen bond O–H···Pt(II): atoms in molecules study and natural bond orbital analysis

In this report, we extended the works of Rizzato et al. [Angew. Chem. Int. Ed. 49, 7440 (2010)] on the nature of O–H···Pt hydrogen bond in trans-[PtCl₂(NH₃)(N–glycine)]·H₂O(1·H₂O) complex, by computational study of O–H···Pt interaction in [NBu₄][Pt(C₆F₅)₃(8-hydroxyquinaldine)], with emphasis on charge transfer effect in this interaction of platinum(II) and hydrogen atom. According to the crystallographic geometry reported by José María Casas et al., [NBu₄][Pt(C₆F₅)₃(8-hydroxyquinaldine)] possesses one O–H···Pt hydrogen bridging interaction, similar to the case in trans-[PtCl₂(NH₃)(N–glycine)]·H₂O(1·H₂O) complex. On the basis of topological criteria of electron density, we characterised this O–H···Pt interaction. Charge transferred between platinum(II) and σ^*_O–H orbital in this complex was calculated by using NBO method. The stabilised energy associated to charge transfer was estimated using a direct proportionality, that is 2–3 eV per electron transferred. Charge transfer effects in O–H···Pt hydrogen bonds were studied for these two complexes. Our results indicate that the interaction of O–H···Pt is closed–shell in nature with significant charge transfer, and that charge transfer effect is not negligible in the interaction of O–H···Pt. The second conclusion is different from the result of Rizzato et al.     

Experimental Investigation into the Low-Molecular-Weight Fluoropolymer for the Storage of Ultracold Neutrons

The experimental setup for examining the low-molecular-weight CF₃(CF₂)₃–O–CF₂–O–(CF₂)₃CF₃ fluoropolymer, which is a promising coating material for the walls of storage chambers for ultracold neutrons, is described. The results are detailed. The measurement data are interpreted in the model of a multilayer complex quantum-mechanical potential of the chamber walls.     

Synthesis of graphene oxide-wrapped core–shell structured carbon sphere@Al2O3 as electrode material for voltammetric determination of butylated hydroxyanisole in food products

Ionics - Here, we report a graphene oxide-wrapped core–shell structured carbon sphere@Al2O3 composite (CS@Al2O3@GO) as the electrode material for sensitive determination of butylated...     

Heat Transfer and Hydrodynamic Performance Analysis of a Miniature Tangential Heat Sink Using Al2O3–H2O and TiO2–H2O Nanofluids

In this article, thermal and hydrodynamic performances of a miniature tangential heat sink are investigated experimentally by using Al₂O₃–H₂O and TiO₂–H₂O nanofluids. The effects of flow rate and volume concentration on the thermal performance have been investigated for the Reynolds number range of 210 to 1,100. Experimental results show that the average convective heat transfer coefficient increases 14 and 11% and the bottom temperature of the heat sink decreases 2.2°C and 1.6°C by using Al₂O₃–H₂O and TiO₂–H₂O nanofluid instead of pure distilled water, respectively.     

In–Ga–Zn–O MESFET with transparent amorphous Ru–Si–O Schottky barrier

Rectifying transparent amorphous Ru–Si–O Schottky contacts to In–Ga–Zn–O have been fabricated by means of reactive sputtering without any annealing processes nor semiconductor surface treatments. The ideality factor, effective Schottky barrier height and rectification ratio are equal to 1.6, 0.9 eV and 10⁵ A/A, respectively. Ru–Si–O/In–Ga–Zn–O Schottky barriers were employed as gate electrodes for In–Ga–Zn–O metal–semiconductor field‐effect transistors (MESFETs). MESFET devices exhibiting on‐to‐off current ratio at the level of 10³ A/A in a voltage range of 2 V, with subthreshold swing equal to 420 mV/dec were demonstrated. A channel mobility of 7.36 cm²/V s was achieved. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterization and Thermal Behaviour of Garnets from Almandine–Pyrope Series at 1200°C

Hyperfine Interactions - The natural garnets from almandine (Fe3Al2Si3O12)–pyrope (Mg3Al2Si3O12) series with the iron to magnesium atomic ratio ranging from 0.2 to 1 were characterised and...     

Theoretical study on the reactions of CH3NHNH2 with ground state O(3P) atom and excited state O(1D) atom

The reaction mechanisms of methylhydrazine (CH₃NHNH₂) with O(³P) and O(¹D) atoms have been explored theoretically at the MPW1K/6-311+G(d,p), MP2/6-311+G(d,p), MCG3-MPWPW91 (single-point), and CCSD(T)/cc-pVTZ (single-point) levels. The triplet potential energy surface for the reaction of CH₃NHNH₂ with O(³P) includes seven stable isomers and eight transition states. When the O(³P) atom approaches CH₃NHNH₂, the heavy atoms, namely N and C atoms, are the favourable combining points. O(³P) atom attacking the middle-N atom in CH₃NHNH₂ results in the formation of an energy-rich isomer (CH₃NHONH₂) followed by migration of O(³P) atom from middle-N atom to middle-H atom leading to the product P6 (CH₃NNH₂+OH), which is one of the most favourable routes. The estimated major product CH₃NNH₂ is consistent with the experimental measurements. Reaction of O(¹D) + CH₃NHNH₂ presents different features as compared with O(³P) + CH₃NHNH₂. O(¹D) atom will first insert into C–H2, N1–H4, and N2–H5 bonds barrierlessly to form the three adducts, respectively. There are two most favourable paths for O(¹D) + CH₃NHNH₂. One is that the C–N bond cleavage accompanied by a concerted H shift from O atom to N atom (mid-N) leads to the product P_I (CH₂O + NH₂NH₂), and the other is that the N–N bond rupture along with a concerted H shift from O to N (end-N) forms P_IV (CH₃NH₂ + HNO). The similarities and discrepancies between two reactions are discussed.     

Optical control and mode selective excitation of coherent phonons in YBa2Cu3O7−δ

Femtosecond time-resolved reflectivity measurement is performed on Y Ba₂Cu₃O_7?δ films. Coherent phonons of both the Ba–O and Cu–O modes are observed at frequencies of 3.4 and 4.3 THz, respectively. Amplitudes of both Ba–O and Cu–O modes are optically manipulated by using a pair of femtosecond pulses, the separation time of which is controlled. Coherent phonons of the Ba–O and Cu–O modes are completely suppressed at the double-pulse separation times of 135.0 and 108.5 fs and those amplitudes are enhanced at 270 and 217 fs, respectively.     

Comparative study of aerogels nanostructured catalysts: Ni/ZrO2–SO4 2− and Ni/ZrO2–Al2O3–SO4 2−

Ionics - A series of Ni/ZrO2–SO4 2− and Ni/ZrO2–Al2O3–SO4 2− catalysts were prepared in one step by the sol–gel method and dried in hypercritical conditions of...     

The catalytic effects of H2CO3, CH3COOH,HCOOH and H2O on the addition reaction of CH2OO + H2O → CH2(OH)OOH

The addition reaction of CH₂OO + H₂O → CH₂(OH)OOH without and with X (X = H₂CO₃, CH₃COOH and HCOOH) and H₂O was studied at CCSD(T)/6-311+ G(3df,2dp)//B3LYP/6-311+G(2d,2p) level of theory. Our results show that X can catalyse CH₂OO + H₂O → CH₂(OH)OOH reaction both by increasing the number of rings, and by adding the size of the ring in which ring enlargement by COOH moiety of X inserting into CH₂OO···H₂O is favourable one. Water-assisted CH₂OO + H₂O → CH₂(OH)OOH can occur by H₂O moiety of (H₂O)₂ or the whole (H₂O)₂ forming cyclic structure with CH₂OO, where the latter form is more favourable. Because the concentration of H₂CO₃ is unknown, the influence of CH₃COOH, HCOOH and H₂O were calculated within 0–30 km altitude of the Earth's atmosphere. The results calculated within 0–5 km altitude show that H₂O and HCOOH have obvious effect on enhancing the rate with the enhancement factors are, respectively, 62.47%–77.26% and 0.04%–1.76%. Within 5–30 km altitude, HCOOH has obvious effect on enhancing the title rate with the enhancement factor of 2.69%–98.28%. However, compared with the reaction of CH₂OO + HCOOH, the rate of CH₂OO···H₂O + HCOOH is much slower.     

Structures,vibrational spectra,and relative energetics of FC(O)ONO and FC(O)NO2 isomers at DFT and ab initio levels

The structural and vibrational parameters of FC(O)ONO and FC(O)NO₂ isomers were examined theoretically using the B3LYP/6-311+G(3df) and CCSD(T)/6-311G(d) methods. Four conformers of FC(O)ONO isomer and one FC(O)NO₂ isomer are found here. Among them, the trans–cis and cis–cis FC(O)ONO configuration are new conformers. The energetics were refined with G3//B3LYP and CBS-QB3 calculations. The trans–trans conformer of the FC(O)ONO isomer is found to be the lowest energy structure, with an estimated heat of formation of ?104.9 kcal mol^?1 at 0 K as determined from CBS-QB3 theory. The next lowest structure is the cis–trans FC(O)ONO lying 1.7 kcal mol^?1 above the trans–trans structural form. The highest energy structure is the FC(O)NO₂ isomer with a predicted heat of formation of ?84.8 kcal mol^?1. A comparison of the relative stability of the FCNO₃ isomers with the isomers of ClCNO₃ shows that the Cl analogues follow the same pattern of stability, as do the F isomers. However, the chlorine isomers are unstable relative to their fluorine analogues.