High‐pressure high‐temperature synthesis of Rh2O3‐II‐type In2O3 polymorph

The metastability of the bixbyite‐ and corundum‐type In₂O₃ polymorphs up to 33 GPa (at room temperature) is shown. While compressed (in diamond anvil cells) and laser‐heated, both polymorphs undergo a phase transition to the Rh₂O₃‐II‐type structure (space group Pbcn, No. 60). The direct transition from bixbyite to Rh₂O₃‐II structure has not yet been observed for any other oxide.

     

In‐situ X‐ray diffraction of mechanically milled β‐Al3Mg2 powders

The structure evolution during heating of mechanically milled single‐phase β‐Al₃Mg₂ has been investigated by in‐situ X‐ray diffraction. The nanoscale supersaturated Al(Mg) solid solution formed during milling transforms back to the original β‐Al₃Mg₂ phase through a sequence of phase transformations. At low temperatures, an increasing amount of Mg is rejected from the solid solution with increasing temperature. At intermediate temperatures, the β′‐phase, a hexagonal phase with approximate composition Al₃Mg₂, forms. Finally, at higher temperatures the original β‐Al₃Mg₂ phase is restored, indicating that the formation of the supersaturated solid solution during milling can be reversed by appropriate heat treatment. The phase transformations during heating are gradual and the temperature ranges of stability of the different structure configurations are quite large, all exceeding 50 K. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High‐temperature stability of Au/p‐type diamond Schottky diode

Rectification properties of Au Schottky diodes were investigated in high‐temperature operation. These diodes were fabricated on a p‐type diamond single crystal using the vacuum‐ultraviolet light/ozone treatment. The ideality factor n of the Schottky diodes decreased monotonically with increasing measurement temperature whereas the Schottky barrier height ?_b increased, and ?_b reached 2.6 eV at 550 K with n of 1.1. Through high temperature heating at 870 K, the mean value of ?_b at 300 K changed permanently from 2.2 eV to 1.1 eV. Decrease of ?_b might originate from a dissolution of oxygen termination at the Au/diamond interface. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Comparing the weak and strong gate‐coupling regimes for nanotube and graphene transistors

We present an experimental and theoretical comparison of the weak and strong gate‐coupling regimes that arise for carbon nanotube (CNT) and graphene field‐effect transistors (FETs) in back‐gated and liquid‐gated configuration, respectively. We find that whereas the back‐gate efficiency is suppressed for a liquid‐gated CNT FET, the back gate is still effective in case of a liquid‐gated graphene FET. We calculate the gate‐induced Fermi‐level shifts and induced charge densities. In both strong and weak coupling regimes, nonlinearities occur in the gate dependence of these parameters, which can significantly influence the electronic transport. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

First principle study of the cation vacancy in anatase TiO2

Based on first principle FP‐LAPW calculations, we have studied the electronic and magnetic properties of anatase TiO₂ with Ti cation vacancy. We find that the Ti cation vacancy defect can induce a magnetic moment of about 4μ_B/supercell. The magnetic moment mainly comes from p‐orbitals of O atoms which surround the Ti vacancy. We also find that the two Ti vacancies in anatase always coupled ferromagnetically. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman study of photo‐induced degradation of the Ru(II) complex adsorbed on nanocrystalline TiO2 films

Photo‐induced degradation of a monolayer of the Ru(II) complex adsorbed on anatase TiO₂ thin films was studied by using resonant micro‐Raman spectroscopy. We developed two contrastive experiments to analyze the degradation mechanism. An exponential decay law was found when the dye was irradiated in the absence of a reducing agent. While the sensitized TiO₂ thin film electrode was covered by the I^–/I₃^– redox couple, the dye degradation exhibited a slowed linear decay. The experimental result was compared and the degradation mechanism was analyzed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mechanistic study on Mo(CO)6‐catalyzed intramolecular [2 + 2] or [2 + 2 + 1] cycloaddition reaction of 5‐allenyl‐1‐ynes

By means of density functional theory, the Mo(CO)₆‐catalyzed intramolecular [2 + 2] or [2 + 2 + 1] cycloaddition reaction of 5‐allenyl‐1‐ynes was investigated. All the intermediates and transition states were optimized completely at B3LYP/6‐311++G(d,p) level (LANL2DZ(f) for Mo). Calculations indicate that the complexation of 5‐allenyl‐1‐ynes with Mo(CO)₆ occurred preferentially at the triple bond to give the complex M1 and then the complexation with the distal double bond of the allenes generates the complex M5 . In this reaction, Mo(CO)₆‐catalyzed intramolecular [2 + 2] cycloaddition is more favorable than [2 + 2 + 1] cycloaddition. The reaction pathway Mo(CO)₆ + R → M5 → T7 → M12 → M13 → T11 → M18 → P4 is the most favorable one, and the most dominant product predicted theoretically is P4 . The solvation effect is remarkable, and it decreases the reaction energy barriers. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermal conductivity of CoSb3 nano‐composites grown via a novel solvothermal nano‐plating technique

We have utilized a solvothermal nano‐plating technique to grow nano‐structured CoSb₃ directly onto the surface of micron‐sized CoSb₃ particles that were subsequently hot pressed and densified into a homogeneous skutterudite nano‐composite. We herein present results for three samples: a bulk sample to serve as a reference, and two samples with solvothermally grown nano‐structures of 5 wt% and 20 wt%, respectively. All three samples used the same bulk starting materials. The thermal conductivity was measured via two independent techniques (steady state and laser flash) and both show a systematic reduction in the thermal conductivity with an increasing amount of nano‐structures. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

First‐principles study on the concentrations of native point defects in high‐dielectric‐constant binary oxide materials

The intrinsic concentrations of point defects in high‐k binary oxide materials of HfO₂, ZrO₂, Y₂O₃ and La₂O₃ are evaluated on the basis of first‐principles calculations. Oxygen defects are found to dominate over a wide range of the oxygen chemical potential. Neutral oxygen vacancies are likely to be responsible for electron trapping in the investigated materials. In HfO₂ and ZrO₂, oxygen Frenkel pairs are likely to form. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A DFT study on the (2 + 3) cycloaddition reactions of 2‐nitropropene‐1 with Z‐C,N‐diarylnitrones

B3LYP/6‐31G* calculations for competing (2 + 3)‐cycloaddition pathways for 2‐nitropropene‐1 (1) to Z‐C, N‐diarylnitrones ( 2a – e ) suggest a concerted reaction mechanism. However, the results point to the strongly asymmetric nature of transition complexes. Increasing polarity of the reaction environment and presence of electron‐donating substituents in the nitrone phenyl rings contribute to the higher asymmetry of these structures. Copyright © 2009 John Wiley & Sons, Ltd.     

Spin–orbit coupling in low‐dimensional gold

We present experimental and theoretical evidence of the role played by the spin–orbit coupling in the electronic structure of a pseudomorphic Au monolayer on Nb(001) substrate. The bands found with the help of the angle‐resolved ultraviolet photoelectron spectroscopy (ARUPS) are compared with those obtained from ab initio self‐consistent calculations by the VASP and WIEN2k codes. The slab calculations are performed including geometric relaxation and using both the generalized‐gradient (GGA) and local‐density (LDA) approximations for the exchange–correlation energy. The dispersions and energy positions of the calculated bands agree with the experimentally determined band structure only if the LDA is used and the spin–orbit coupling is included. Therefore, both the structure relaxation and spin–orbit coupling are essential in understanding the electronic structure of the Au/Nb(001) system.

     

Negative refraction of low‐frequency electromagnetic waves

Features of anomalous refraction of low‐frequency electromagnetic waves are investigated in all‐semiconductor nonmagnetic superlattices with a periodic array of two‐dimensional electron gas layers under quantum Hall effect conditions. We show that the structure exhibits negative refraction on the lateral surface for all angles of incidence, in the frequency region which has no limitation from the low‐frequency side, and that for such intriguing properties it requires no resonance frequency and no negative component of the permittivity tensor. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Stereoselectivity and kinetics of [4 + 2] cycloaddition reaction of cyclopentadiene to para‐substituted E‐2‐arylnitroethenes

In spite of diversified electrophilicity of E‐2‐arylnitroethenes, their [4 + 2] cycloaddition reactions with cyclopentadiene leads to the corresponding 6‐endo‐aryl‐5‐exo‐nitronorbornenes and 6‐exo‐aryl‐5‐endo‐nitronorbornenes as the only reaction products. Stereoselectivity, substituent and solvent effects, and activation parameters, suggest that these reactions occur via a synchronous concerted mechanism on both competing pathways. The experimental results obtained are consistent with the data from B3LYP/6‐31G(d) calculations. Due to high electrophilicity of E‐2‐arylnitroethenes, the reactions studied should be considered as polar [4 + 2] cycloadditions. Copyright © 2011 John Wiley & Sons, Ltd.     

First‐principle investigation of strain effects on the electronic properties of germanium nanowires

Using the GGA functional in density functional theory, the effects of axial strain on the band structure and effective mass of narrow [110] and [100] germanium nanowires are investigated. It is observed that both compressive and tensile strain cause indirect‐to‐direct bandgap transitions. One percent of tensile strain can cause a 40 meV change in the bandgap of [110] nanowires. Effective masses of electrons and holes are subject to a change of 3–4 times in the strain‐induced transition point. This change translates into a density of state modulation which opens new possibilities for the construction of Ge nanowire‐based sensors. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Decay Dynamics of 3‐methyl‐3‐pentene‐2‐one from the light absorbing S2(ππ*) state ‐ Resonance Raman Spectroscopy and CASSCF Study

The photophysics of 3‐methyl‐3‐pentene‐2‐one (3M3P2O) after excitation to the S₂(ππ*) electronic state were studied using the resonance Raman spectroscopy and complete active space self‐consistent field (CASSCF) method calculations. The A‐band resonance Raman spectra were obtained in cyclohexane, acetonitrile, and methanol with excitation wavelengths in resonance with the first intense absorption band to probe the structural dynamics of 3M3P2O. The B3LYP‐TD/6‐31++G(d, p) computation was carried out to determine the relative A‐band resonance Raman intensities of the fundamental modes, and the result was used to reproduce the corresponding fundamental band intensities of the 223.1 nm resonance Raman spectrum and thus to examine whether the vibronic‐coupling existed in Franck‐Condon region or not. CASSCF calculations were carried out to determine the minimal singlet excitation energies of S_{1, FC}, S_1,min (nπ*), S_{2, FC}, S_2,min (ππ*), the transition energies of the conical intersection points S_n/S_π, S_n/S₀, and the optimized excited state geometries as well as the geometry structures of the conical intersection points. The A‐band short‐time structural dynamics and the corresponding decay dynamics of 3M3P2O were obtained by the analysis of the resonance Raman intensity pattern and CASSCF computations. It was revealed that the initial structural dynamics of 3M3P2O was towards the simultaneous C₃=C₄ and C₂=O₇ bond elongation, with the C₃=C₄ bond length lengthening greater at the very beginning, whereas the C₂=O₇ bond length changing greater at the later evolution time before reaching the CI(S₂/S₁) conical intersection point. The decay dynamics from S₂(ππ*) to S₁(nπ*) via S₂(ππ*)/S₁(nπ*) in singlet realm and from S₁(nπ*) to T₁(nπ*) via ISC[S₁(nπ*)/T₂(ππ*)/T₁(nπ*)] in triplet realm are proposed. Copyright © 2014 John Wiley & Sons, Ltd.     

Investigation of cation–anion interaction in 1‐(2‐hydroxyethyl)‐3‐methylimidazolium‐based ion pairs by density functional theory calculations and experiments

Gas‐phase structure, hydrogen bonding, and cation–anion interactions of a series of 1‐(2‐hydroxyethyl)‐3‐methylimidazolium ([HOEMIm]⁺)‐based ionic liquids (hereafter called hydroxyl ILs) with different anions (X = [NTf₂]^–, [PF₆]^–, [ClO₄]^–, [BF₄]^–, [DCA]^–, [NO₃]^–, [AC]^– and [Cl]^–), as well as 1‐ethyl‐3‐methylimizolium ([EMIm]⁺)‐based ionic liquids (hereafter called nonhydroxyl ILs), were investigated by density functional theory calculations and experiments. Electrostatic potential surfaces and optimized structures of isolated ions, and ion pairs of all ILs have been obtained through calculations at the Becke, three‐parameter, Lee–Yang–Parr/6‐31 + G(d,p) level and their hydrogen bonding behavior was further studied by the polarity and Kamlet–Taft Parameters, and ¹H‐NMR analysis. In [EMIm]⁺‐based nonhydroxyl ILs, hydrogen bonding preferred to be formed between anions and C2–H on the imidazolium ring, while in [HOEMIm]⁺‐based hydroxyl ILs, it was replaced by a much stronger one that preferably formed between anions and OH. The O–H···X hydrogen bonding is much more anion‐dependent than the C2–H···X, and it is weakened when the anion is changed from [AC]^– to [NTf₂]^–. The different interaction between [HOEMIm]⁺ and variable anion involving O–H···X hydrogen bonding resulted in significant effect on their bulk phase properties such as ¹H‐NMR shift, polarity and hydrogen‐bond donor ability (acidity, α). Copyright © 2011 John Wiley & Sons, Ltd.     

In‐situ synthesis of transparent and conductive carbon nanotube networks

A method for the production of transparent carbon nanotube networks (CNTNs) over transparent substrates was developed. In this method, CNTNs were grown directly in the target surface by applying the catalyst in specific zones of the substrate through lithographic techniques. The networks can be also transferred from the original substrate to other surfaces. The newly grown carbon nanotubes have a very high aspect ratio (>50000). Thus far, networks with an optical transmittance of 94% at 550 nm and a surface resistivity of 3.6 kΩ/sq have been produced. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Time‐resolved ultrafast carrier dynamics in as‐grown nanocrystalline silicon films: the effect of film thickness and grain boundaries

In this letter, we have studied transient photoinduced absorption in as‐grown nanocrystalline silicon films with thickness varied from 5 to 30 nm. Effects of quantum confinement (QC) in z ‐direction and grain boundary distortions alter the carrier dynamics of these films considerably. Based on the determination of critical points in the first Brillouin zone of the band structure of materials, we have time‐resolved the relaxation times of surface‐related states and indirect valleys. When decreasing the film thickness down to the QC limit (∼10 nm) new ultrafast relaxation mechanisms start to play a dominant role in carrier dynamics due to the topological disordering of these ultrathin films. These relaxation mechanisms seem to be related with the traping/de‐traping of the excited carriers prior to recombination. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The β‐silicon effect. 4: substituent effects on the solvolysis of 1‐alkyl‐2‐(aryldimethylsilyl)ethyl trifluoroacetates

Solvolysis rates of 2‐(aryldimethylsilyl)‐1‐methylethyl and 2‐(aryldimethylsilyl)‐1‐tert‐butylethyl trifluoroacetates were determined conductimetrically in 60% (v/v) aqueous ethanol. The effects of aryl substituents at the silicon atom on the solvolysis rates at 50 °C were correlated with parameters of r⁺ = 0.15 with the Yukawa–Tsuno equation, giving ρ values of ?1.5 for both secondary α‐Me and α‐tert‐Bu systems. The ρ values for those secondary systems are less negative than ?1.75 for the 2‐(aryldimethylsilyl)ethyl system that proceeds by the Eaborn (non‐vertical) mechanism, while they are distinctly more negative than ?0.99 for 2‐(aryldimethylsilyl)‐1‐phenylethyl system that should proceed by the Lambert (vertical) mechanism. There was a fairly linear relationship between the reaction constants (ρ) for the β‐silyl substituent effects and the solvolysis reactivities for a series of β‐silyl substrates. The solvolyses of the α‐Me and tert‐Bu substrates proceed through the transition state (TS) with an appreciable degree of the β‐silyl participation, close to the Eaborn (non‐vertical) TS rather than to the Lambert (vertical) TS. Copyright © 2010 John Wiley & Sons, Ltd.     

Enhanced piezoelectric properties of sodium bismuth titanate (Na0.5Bi4.5Ti4O15) ceramics with B‐site cobalt modification

The piezoelectric properties of the cobalt‐modified sodium bismuth titanate (Na_0.5Bi_4.5Ti₄O₁₅, NBT) piezoelectric ceramics were investigated. The piezoelectric properties of NBT ceramics were significantly enhanced by cobalt modification. The Curie temperature T_C and piezoelectric constant d₃₃ for the 0.3 wt% cobalt‐modified NBT ceramics (NBT‐C3) were found to be 663 °C and 30 pC/N, respectively. Thermal annealing studies presented that the cobalt‐modified NBT ceramics possess stable piezoelectric properties, demonstrating that the cobalt‐modified NBT‐based ceramics are promising candidates for high temperature piezoelectric applications. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)