Na‐site energy of P2‐type NaxM O2 (M = Mn and Co)

P2‐type Na_xM O₂ (M = Mn and Co) is a promising cathode material for low‐cost sodium ion secondary batteries. In this structure, there are two different crystallographic Nai (i = 1 and 2) sites with different Coulomb potential $ (\varphi _i)$ provided by M^4–x and O^2–. Here, we experimentally determine a difference ${(\rm \Delta }\varepsilon \equiv \varepsilon _1 - \varepsilon _2)$ of Na‐site energies ${(}\varepsilon _i \equiv e\varphi {\kern 1pt} _i)$ based on the temperature dependence of the site occupancies. We find that ${\rm \Delta }\varepsilon \;{=}\;56\;{K}$ for Na_0.52MnO₂ is significantly smaller than 190 K for Na_0.59CoO₂. We interpret the suppressed ${\rm \Delta }\varepsilon $ in Na_0.52MnO₂ in terms of the screening effect of the Na⁺ charge. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

An ab initio study of CX3‐substitution (X = H,F, Cl,Br, I) effects on the static electric polarizability and hyperpolarizability of diacetylene

We report a systematic ab initio and density functional theory (DFT) study of the electric properties of the X₃C? C≡C? C≡C? H (X = H, F, Cl, Br, and I) sequence of substituted diacetylenes. We rely on finite‐field Møller–Plesset perturbation theory and coupled‐cluster calculations with large, flexible basis sets. Our best values at the second‐order Møller–Plesset perturbation theory level for the mean dipole polarizability and second hyperpolarizability are $\overline {{\alpha} } $ /e²aE = 64.46 (? CH₃), 65.59 (? CF₃), 110.11 (? CCl₃), 138.90 (? CBr₃), 184.98 (? CI₃) and $\overline {{\gamma} } $ /e⁴aE = 21020 (? CH₃), 13469 (? CF₃), 32708 (? CCl₃), 57599 (? CBr₃), and 105251 (? CI₃). For comparison, the analogous MP2 values for diacetylene [P.Karamanis and G.Maroulis, Chem. Phys. Lett. 2003 , 376, 403.] are $\overline {{\alpha} } $ /e²aE = 49.17, and $\overline {{\gamma} } $ /e⁴aE = 16227. For the mean first hyperpolarizability we report $\overline {{\beta} } $ /e³aE = ?205.8 (? CH₃), ?55.7 (? CF₃), 120.8 (? CCl₃), 443.8 (? CBr₃), and 725.4 (? CI₃). Copyright © 2010 John Wiley & Sons, Ltd.     

DFT study and NBO analysis of the mutual interconversion of cumulene compounds

The B3LYP/6‐31G* method was used to investigate the configurational properties of allene (1,2‐propadiene) ( 1 ), 1,2,3‐butatriene ( 2 ), 1,2,3,4‐pentateriene ( 3 ), 1,2,3,4,5‐hexapentaene ( 4 ), 1,2,3,4,5,6‐heptahexaene ( 5 ), 1,2,3,4,5,6,7‐octaheptaene ( 6 ), 1,2,3,4,5,6,7,8‐nonaoctaene ( 7 ), and 1,2,3,4,5,6,7,8,9‐decanonaene ( 9 ). The calculations at the B3LYP/6‐31G* level of theory showed that the mutual interconversion energy barrier in compounds 1 – 8 are: 209.73, 131.77, 120.34, 85.00, 80.91, 62.19, 55.56, and 46.83 kJ mol^?1, respectively. The results showed that the difference between the average C?C double bond lengths ( ) values in cumulene compounds 1 and 2 , is larger than those between 7 and 8 , which suggest that with large n (number of carbon atoms in cumulene chain), the values approach a limiting value. Accordingly, based on the plotted data, the extrapolation to n = ∞, gives nearly the same limiting (i. e., ). Also, NBO results revealed that the sum of π‐bond occupancies, , decrease from 1 to 8 , and inversely, the sum of π‐antibonding orbital occupancies, , increase from compound 1 to compound 8 . The decrease of values for compounds 1 – 8 , is found to follow the same trend as the barrier heights of mutual interconversion in compounds 1 – 8 , while the decrease of the barrier height of mutual interconversion in compounds 1 – 8 is found to follow the opposite trend as the increase in the number of carbon atom. Accordingly, besides the previously reported allylic resonant stabilization effect in the transition state structures, the results reveal that the values, , Δ(E_HOMO ? E_LUMO), and the C atom number could be considered as significant criteria for the mutual interconversion in cumulene compounds 1 – 8 . This work reports also useful predictive linear relationships between mutual interconversion energy barriers ( ) in cumulene compounds and the following four parameters: , , Δ(E_HOMO ? E_LUMO), and C_Number. Copyright © 2007 John Wiley & Sons, Ltd.     

Epitaxy of m ‐plane ZnO on (112) LaAlO3 substrate

Heteroepitaxial growth of non‐polar m ‐plane (10 0) ZnO has been demonstrated on (112) LaAlO₃ single crystal substrates using the pulsed laser deposition method. X‐ray diffraction, reflection high energy electron diffraction, and cross‐sectional transmission electron microscopy with selected‐area diffraction, have been used to characterize the structural properties of deposited ZnO films. The epitaxial relationship between ZnO and LAO is shown to be (10 0)_ZnO ∥ (112)_LAO, (11 0)_ZnO ∥ ( 1)_LAO and [0001]_ZnO ∥ [ 10]_LAO. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hierarchy of the non‐covalent interactions in the alanine‐based secondary structures. DFT study of the frequency shifts and electron‐density features

The alanine (Ala)‐based cluster models of C5, C7, and C10 H‐bonds are studied at the DFT/B3LYP level. CPMD/BLYP simulations of the infinite polyalanine α‐helix (C13 H‐bond) and the two‐stranded β‐sheets are performed. Combined use of frequency shifts and electron‐density features enable us to detect and describe quantitatively the non‐covalent interactions (H‐bonds) defining the intrinsic properties of Ala‐based secondary structures. The energies of the primary N? H O H‐bonds are decreasing in the following way: C13 > C5 ≥ C7 > C10. The energies of the secondary N? H O, N?H N, and H H interactions are comparable to those of the primary H‐bonds (～4.5 kcal/mol). Side chain–backbone C? H O interaction is found to be the weakest non‐covalent interaction in the considered species. Its energy is ～0.5 kcal/mol in the infinite polyalanine α‐helix. Quantum‐topological electron‐density analysis is found to be a powerful tool for the detection of secondary non‐covalent interactions (C?O H? C and H H) and bifurcated H‐bonds, while the frequency shift study is useful for the identification and characterization of primary or secondary H‐bonds of the N? H O type. Copyright © 2008 John Wiley & Sons, Ltd.     

Single domain nonpolar (13$ \bar 4 $0) ZnO on (114) LaAlO3

An unconventional nonpolar plane (13$ \bar 4 $ 0) ZnO epitaxial film was grown on a 2‐inch (114) LaAlO₃ (LAO) substrate by pulsed laser deposition. Reflection high energy electron diffraction (RHEED) patterns of the grown ZnO surface demonstrate single crystalline characteristics with the orientation inclined with the a‐axis. Atomic force microscopy (AFM) shows that the grown ZnO film exhibits a stripe‐like surface morphology with the longitudinal direction parallel to the c‐axis. Cross‐sectional transmission electron microscopy (TEM) with selected area electron diffraction (SAED) was used to characterize the microstructure and to determine the growth plane of ZnO grown film as (13$ \bar 4 $ 0). In addition, XRD pole‐figure measurements confirm the single domain growth of (13$ \bar 4 $ 0) ZnO on (114) LAO. Room temperature photoluminescence spectra of the ZnO film measured across the substrate show the same near band edge emission peak at 3.29 eV, indicating that the nonpolar (13$ \bar 4 $ 0) ZnO film has excellent uniform optical properties. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Theoretical study of the initial stage of InN growth on cubic zirconia (111) substrates

An initial stage of InN growth on cubic zirconia (111) substrates has been investigated using first‐principles calculations based on density functional theory (DFT). We have evaluated adsorption energies of indium and nitrogen atoms on cubic zirconia (111) surfaces, and have found that the differences in the adsorption energies of the indium atoms at various adsorption sites were small, indicating that the migration of the indium atoms on zirconia (111) surfaces occurs readily. On the other hand, we have found that the differences in the adsorption energies of the nitrogen atoms at various adsorption sites were large, implying that the nitrogen atoms tend to stay at the stable site with the largest adsorption energy, which was identified as the O–Zr bridge site. These results suggest that the first layer of InN films is the nitrogen layer. In addition, we have found that the energetically favorable arrangement is comprised of InN(0001)//cubic zirconia (111) and InN $ [11\bar 20] $ //cubic zirconia $ [1 \bar 10], $ which is quite consistent with previously obtained experimental data. Furthermore, the hybridization effect between N 2p and O 2p plays a crucial role in determining the interface structure for the growth of InN on cubic zirconia (111) surfaces. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman scattering and disorder effect in Cu2ZnSnS4

The Raman spectra of surface regions of bulk Cu₂ZnSnS₄ (CZTS) samples with different Cu and Zn cation content were obtained and the differences in the spectra are attributed to statistical disorder effects in the cation sublattice. This disorder in the Cu and Zn sublattices may initiate a change of the crystal symmetry from kesterite‐type $({I\bar 4})$ to $({I\bar 42m})$ space group. The investigated CZTS crystals grown at high temperature are characterised by the co‐existence of regions with different composition ratio of Cu/(Zn + Sn) which results in kesterite and disordered kesterite phases. The presence of a disordered phase with ${I\bar 42m}$ symmetry is reflected in the appearance of a dominant broadened A‐symmetry peak at lower frequency than the peak of the main A‐symmetry kesterite mode at 337 cm^–1. We suppose that due to a small energy barrier between these phases the transition from one phase to the other can be stimulated by optical excitation of Cu₂ZnSnS₄. The analysis of the Raman spectra measured under different excitation conditions has allowed obtaining first (to our knowledge) experimental evidence of the existence of such optically induced structural transition in CZTS. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Silver: a novel growth catalyst for Ge nanoislands on Si(113)

The impact of silver pre‐adsorption on germanium growth on Si(113) was investigated using in‐situ low‐energy electron microscopy (LEEM) as well as low‐energy electron diffraction (LEED). The adsorption of silver leads to the formation of a regular pattern of nanofacets along the [1 0] direction. The periodicity of this pattern in [33 ] direction was determined to (44 ± 4) nm. From LEED series at different energies the facets were identified to be of (111) and (115) orientation. While the (111) facets show a (√3 × √3)‐R30° reconstruction, the (115) facets exhibit a (2 × n) superstructure. The subsequent growth of Ge results in the formation of nanoislands that are aligned along the facets. These Ge islands have an anisotropic shape with typical sizes of about 100 nm in [33 ] direction and 400 nm in [1 0] direction. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of growth stoichiometry on the structural properties of AlN films on thermally nitrided sapphire $(11\bar 20)$

High‐quality AlN epilayers were grown via pulsed sputtering deposition on thermally nitrided sapphire $(11\bar 20)$ with precise control of the N/Al ratio. Under slightly Al‐rich growth conditions, the growth of AlN epilayers on the thermally nitrided sapphire proceeded in a two‐dimensional mode from the initial stage of growth, and their surfaces were atomically flat stepped and terraced structures. The FWHM values of the X‐ray rocking curves were as low as 87 arcsec and 339 arcsec for the 0002 and $1 \bar 102$ diffractions, respectively, at a film thickness of 400 nm. The present approach is therefore quite promising for the low‐cost fabrication of AlGaN‐based UV optical devices. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Substituent effect on the UV spectra of p‐disubstituted compounds XPh(CHCHPh)nY (n = 0, 1, 2)

Three parameters, , and , are developed to express the substituent effect and the effect of the parent molecular structure of p‐disubstituted compounds XPh(CH?CHPh)_nY (n = 0, 1, 2). The investigated result shows a good correlation between the UV absorption wavenumbers (υ_max) and the three parameters for a diverse set of title compounds, and the correlation equation can be used to predict the UV absorption energy of compounds with the mentioned structure. This approach provides a new insight for the quantitative structure‐property relationship (QSPR) correlation of the UV absorption energy of p‐disubstituted homologues. Copyright © 2010 John Wiley & Sons, Ltd.     

Kinetics and mechanisms of gas‐phase elimination of 2,2‐diethoxyethyl amine and 2,2‐diethoxy‐N,N‐diethylethanamine

The gas‐phase elimination kinetics of 2,2‐diethoxyethyl amine and 2,2‐diethoxy‐N,N‐diethylethanamine (320–380 °C; 40–150 Torr) in a seasoned reaction vessel are homogeneous, unimolecular and obey a first‐order rate law. These elimination processes involve two parallel reactions. The first gives ethanol and the corresponding 2‐ethoxyethenamine. The latter compound further decomposes to ethylene, CO and the corresponding amine. The second parallel reaction produce ethane and the corresponding ethyl ester of an α‐amino acid. The following Arrhenius expressions are given as: For 2,2‐diethoxyethyl amine For 2,2‐diethoxy‐N,N‐diethylethanamine Comparative kinetic and thermodynamic parameters of the overall, the parallel and the consecutive reactions lead to consider two types of mechanisms in terms of a concerted polar cyclic transition state structures. Copyright © 2008 John Wiley & Sons, Ltd.     

Epitaxial phase‐change materials

Epitaxial $ {\rm Ge}_{2} {\rm Sb}_{2} {\rm Te}_{5} $ thin layers were successfully grown in the metastable cubic phase on both slightly lattice‐mismatched (GaSb) and highly lattice‐mismatched (Si) templates. The higher quality of the films grown on (111)‐oriented substrates is attributed to the tendency to form layered structures in the stable bulk phase as well as to the nature of distortion in the metastable cubic phase. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structures of 3‐methyl‐2(1H)‐quinoxalinone and three substituted derivatives

3‐Methyl‐2(1H)‐quinoxalinone and three derivatives (3,7‐dimethyl‐2(1H)‐quinoxalinone, 3‐methyl‐6,7‐dichloro‐2(1H)‐quinoxalinone and 3‐methyl‐7‐nitro‐2(1H)‐quinoxalinone) have been synthesised and analysed by ¹H NMR and IR spectral spectroscopies. The crystal structures have been determined at room temperature from X‐ray single crystal diffraction data for three of them and from powder diffraction data for the nitro derivative. 3‐Methyl‐2(1H)‐quinoxalinone crystallises in the P2₁/c monoclinic system, 3,7‐dimethyl‐2(1H)‐quinoxalinone in the Pbca orthorhombic system and the two others compounds in the P$\overline {1} $ triclinic system. For the nitro derivative, C? H$\cdots $ N short contacts are established between the carbon of the methyl and the double bounded nitrogen of the ring. For the three other compounds N? H$\cdots $ O hydrogen bonds involve the atoms of the heterocyclic ring. Copyright © 2011 John Wiley & Sons, Ltd.     

From RHIC to LHC: a relativistic diffusion approach

We investigate the energy dependence of stopping and hadron production in high‐energy heavy‐ion collisions based on a three‐sources Relativistic Diffusion Model. The transport coefficients are extrapolated from Au + Au and Cu + Cu at RHIC energies ( = 19.6–200 GeV) to Pb + Pb at LHC energies = 5.52 TeV. Rapidity distributions for net protons, and pseudorapidity spectra for produced charged particles in central collisions are compared to data at RHIC energies, and discussed for several extrapolations to LHC energies.     

Structure and reactivity in the hydrolyses of aliphatic carboxylic acid esters and chlorides

For hexanoic acid and its seven isomers, relative rates have been determined for acid catalysed esterification with methanol, and compared with those for saponification of the methyl esters. A good correlation between logarithms of relative rates for the two reactions is obtained, and it is suggested that the eight isomers provide a test set of compounds in which steric effects alone act on reactivity at the acyl carbon. A full set of steric parameters ( values) are presented. Rates of solvolyses of the acid chlorides of the isomers have been determined conductometrically in 3:1 wt:wt acetonitrile water. Logarithms of relative rates show a poor correlation with , and, taking into account the solvent dependence of the rates, the pattern excludes both rate‐limiting formation of a tetrahedral intermediate and rate‐limiting dissociation of chloride to form acylium ions. The remaining possibilities, a concerted process (A_ND) and rapid reversible formation of a hydrate followed by rate‐limiting dissociation of chloride (A_N + D) are considered. Copyright © 2007 John Wiley & Sons, Ltd.     

Growth of InN films on spinel substrates by pulsed laser deposition

We have grown InN films on MgAl₂O₄(111) substrates with atomically flat surfaces using pulsed laser deposition (PLD) and compared their structural properties with those grown on (Mn,Zn)Fe₂O₄(111) substrates. It has been revealed that InN(0001) films grow on MgAl₂O₄(111) with an in‐plane epitaxial relationship of InN[1 00] // MgAl₂O₄[1 0], achieving a lattice mismatch minimum. The InN films exhibited a clear sixfold rotational symmetry, without 30° rotational domains and with a full width at half maximum value of the InN 0002 rocking curve being 17.5 arcmin. Comparison between InN films grown on MgAl₂O₄ and those on (Mn,Zn)Fe₂O₄ led us to conclude that suppression of the interfacial reactions between the InN films and the substrate is inherently important to obtain high quality InN on substrates with a spinel structure. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Kinetics and thermodynamics of the Li/Li+ couple in tetrahydrofuran at low temperatures (195–295 K)

Kinetic and thermodynamic (formal potential) data relating to the synthetically useful Li/Li⁺ couple in tetrahydrofuran (THF) solvent at a range of temperatures (196–295 K) are reported. Formal potentials, have been measured versus the standard reference electrode, in THF. At 295 K the following data have been obtained using a mathematical model to simulate the electro‐deposition (metal deposition and growth kinetics) processes of lithium (Li) on a platinum microelectrode; a of ?3.48 ± 0.005 V, = ?9.2 (±0.5) × 10^?4 V K^?1, the standard electrochemical rate constant, k₀ = 1 (± 0.1) × 10^?4 cm s^?1, transfer coefficient, α = 0.57 ± 0.03 and diffusion coefficient, D = 8.7 ± 0.1 × 10^?6 cm² s^?1. Copyright © 2007 John Wiley & Sons, Ltd.     

The mechanisms of the homogeneous,unimolecular, elimination kinetics of several β‐substituted diethyl acetals in the gas‐phase

The rates of gas‐phase elimination of several β‐substituted diethyl acetals have been determined in a static system and seasoned with allyl bromide. The reactions, inhibited with toluene, are homogeneous, unimolecular, and follow first‐order law kinetics. These elimination processes involve two parallel reactions. The first parallel reaction yields ethanol and the corresponding ethyl vinyl ether. The latter product is an unstable intermediate and further decomposes to ethylene and the corresponding substituted aldehyde. The second parallel reaction gives ethane and the corresponding ethyl ester. The kinetics has been measured over the temperature range of 370–441 °C and pressure range of 23–160 torr. The rate coefficients are given by the following Arrhenius equations: The differences in the rates of ethanol formation may be attributed to electronic transmission of the β‐substituent. The comparative kinetic and thermodynamic parameters of the parallel reactions suggest two different concerted polar four‐membered cyclic transition state types of mechanisms. Copyright © 2010 John Wiley & Sons, Ltd.     

A novel probe for determination of electrical surface potential of surfactant micelles: N,N'‐di‐n‐octadecylrhodamine

The peculiarities of the structure of the fluorescent dye N,N'‐di‐n‐octadecylrhodamine advantage its using as an interfacial acid–base probe in aqueous micellar solution of colloidal surfactants. Two long hydrocarbon tails of the dye provide similar orientation of both cation and zwitterion on the micelle/water interface, with the ionizing group COOH exposed to the Stern region in all the systems studied. Further, the charge type of the acid–base couple, A⁺B^±, ensures similar values of the ‘intrinsic’ contribution, pK, to the ‘apparent’ pK value in micelles of different surfactants. This makes the indicator suitable for determination of electrical surface potentials, Ψ. The pKs have been obtained in cationic, anionic, zwitterionic, and nonionic surfactant systems, at various salt background. In total 17 systems were studied. At bulk counterion concentration of ca. 0.05 M, the pK values vary from 2.14 ± 0.07 in n–C₁₈H₃₇N(CH₃)Cl^– micelles to 5.48 ± 0.06 in n–C₁₆H₃₃OSONa⁺ micelles. The Ψ values, corresponding to the Stern region of micelles, have been evaluated as Ψ = 59.16 pK–pK for T = 298.15 K. The pK parameter was equated to the average value of 4.23 in nonionic surfactants (4.12–4.32, depending on the surfactant type). For cetyltrimethylammonium bromide and sodium n‐dodecylsulfate micelles, the Ψ values (±(7–11) mV) appeared to be +118 mV and at bulk Br^? concentration 0.019 M and ?76 mV at bulk Na⁺ concentration 0.020 M, respectively. This satisfactorily agrees with the theoretical values +111 and ?84 mV, estimated using the Oshima, Healy, and White equation for these well‐defined colloidal systems. Finally, not only absorption, but also fluorescence spectra display the same response to changes in bulk pH. Copyright © 2007 John Wiley & Sons, Ltd.