Natural Bond Orbital Study on the Nature of Binding in the H2 Molecule

We use the natural bond orbital (NBO) method to decompose a MO wavefunction into the intuitive valence bond (VB) structures. At least two natural orbital type MO are required to describe the essential binding of the H₂ molecule at all inter nuclear distances. At first the MO wavefunction is transformed into an unrestricted Hartree-Fock wave-function consisted of non-orthogonal localized orbitals u' and v', and then the NBO method is used to decompose u' and v' into the physical meaningful orthogonal localized orbitals. Our results show that the orbitals u' and v' are decomposed into an atomic and an overlap parts. The latter part gives rise to the conventional ionic structure in the VB picture.     

Whole‐Cell Photoenzymatic Cascades to Synthesize Long‐Chain Aliphatic Amines and Esters from Renewable Fatty Acids

Long‐chain aliphatic amines such as (S,Z)‐heptadec‐9‐en‐7‐amine and 9‐aminoheptadecane were synthesized from ricinoleic acid and oleic acid, respectively, by whole‐cell cascade reactions using the combination of an alcohol dehydrogenase (ADH) from Micrococcus luteus, an engineered amine transaminase from Vibrio fluvialis (Vf‐ATA), and a photoactivated decarboxylase from Chlorella variabilis NC64A (Cv‐FAP) in a one‐pot process. In addition, long chain aliphatic esters such as 10‐(heptanoyloxy)dec‐8‐ene and octylnonanoate were prepared from ricinoleic acid and oleic acid, respectively, by using the combination of the ADH, a Baeyer–Villiger monooxygenase variant from Pseudomonas putida KT2440, and the Cv‐FAP. The target compounds were produced at rates of up to 37 U g^?1 dry cells with conversions up to 90 %. Therefore, this study contributes to the preparation of industrially relevant long‐chain aliphatic chiral amines and esters from renewable fatty acid resources.     

Mesoporous Titania Thin Film with Highly Ordered and Fully Accessible Vertical Pores and Crystalline Walls

We report the preparation of mesoporous titania thin films with the R m pore structure derived from the Im m self‐assembled ordering of the titania species and an EO₁₀₆PO₇₀EO₁₀₆ triblock copolymer. The films were spin‐cast and then aged at 18 °C at a relative humidity of 70 %, which led to the orientation of the Im m structure with the [111] direction perpendicular to the substrates. The [111] body‐diagonal channels became vertical channels upon calcination at 400 °C, thus leading to thin films with vertical channels. The pores are ordered over a large area of up to 1 μm². The titania films can be formed on various types of substrates. By using a titania film formed on a Pt‐coated Si wafer as a template, we produced by an electrochemical‐deposition technique arrays of gold nanowires, whose morphology suggests that most of the pores of the titania thin films are accessible. The pore structure of vertical channels is stable up to 600 °C, at which temperature the wall materials crystallize into anatase.     

Fabrication and transmission experiments of distributed feedback laser modules for 2.5 Gb s-1 optical transmission systems

A distributed feedback (DFB) laser module has been developed for 2.5 Gbs^-1 optical transmission systems. The DFB laser has a multiple-quantum-well (MQW) active layer and a planar buried heterostructure (PBH) for a low threshold current and stable singlemode operation with low chirping. A PBH DFB laser module with a single-mode fibre pigtail and an optical isolator was designed and fabricated by employing a single lens and a laser welding method. The fabricated MQW PBH DFB laser module is shown to be a suitable light source for 2.5 Gb s^-1 optical transmission systems with a minimum received power of-33 dBm after 47 km conventional optical fibre transmission.     

Asymmetry in electrical properties of Al‐doped TiO2 film with respect to bias voltage

The energy diagram of RuO₂/Al‐doped TiO₂/RuO₂ structures was estimated from the capacitance–voltage and leakage current density–voltage curves. The Al‐doping profile in TiO₂ film was varied by changing position of the atomic layer deposition cycle of Al₂O₃ during the atomic layer deposition of 9 nm‐thick TiO₂ film. The interface between the TiO₂ film and the RuO₂ electrode containing Al‐doping layer showed a higher Schottky barrier by 0.1 eV compared with the opposite interface without the doping layer. The evolution of various leakage current profiles upon increasing the bias with opposite polarity could be well explained by the asymmetric Schottky barrier. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Measurement of scattering rate and minimum conductivity in graphene

The conductivity of graphene samples with various levels of disorder is investigated for a set of specimens with mobility in the range of 1-20x10(3) cm2/V sec. Comparing the experimental data with the theoretical transport calculations based on charged impurity scattering, we estimate that the impurity concentration in the samples varies from 2-15x10(11) cm(-2). In the low carrier density limit, the conductivity exhibits values in the range of 2-12e2/h, which can be related to the residual density induced by the inhomogeneous charge distribution in the samples. The shape of the conductivity curves indicates that high mobility samples contain some short-range disorder whereas low mobility samples are dominated by long-range scatterers.     

Neutrons and antiprotons in ultrahigh-energy cosmic rays

The neutron fraction in the very high-energy cosmic rays near the Greisen-Zatsepin-Kuzmin (GZK) cutoff energy is analyzed by taking into account the time dilation effect of the neutron decays and also the pion photoproduction behaviors above the GZK cutoff. We predict a non-trivial neutron fraction above the GZK cutoff and a negligibly small neutron fraction below. However, there should be a large antiproton fraction in the high-energy cosmic rays below the GZK cutoff in several existing models for the observed cosmic-ray events above and near the GZK cutoff. Such a large antiproton fraction can manifest itself by the muon charge ratio μ⁺/μ^- in the collisions of the primary nucleon cosmic rays with the atmosphere, if there is no neutron contribution. We suggest to use the muon charge ratio as one of the information to detect the composition of the primary cosmic rays near or below the GZK cutoff.     

Diffusion, coalescence, and reconstruction of vacancy defects in graphene layers

Diffusion, coalescence, and reconstruction of vacancy defects in graphene layers are investigated by tight-binding molecular dynamics (TBMD) simulations and by first principles total energy calculations. It is observed in the TBMD simulations that two single vacancies coalesce into a 5-8-5 double vacancy at the temperature of 3000 K, and it is further reconstructed into a new defect structure, the 555-777 defect, by the Stone-Wales type transformation at higher temperatures. First principles calculations confirm that the 555-777 defect is energetically much more stable than two separated single vacancies, and the energy of the 555-777 defect is also slightly lower than that of the 5-8-5 double vacancy. In TBMD simulation, it is also found that the four single vacancies reconstruct into two collective 555-777 defects which is the unit for the hexagonal haeckelite structure proposed by Terrones et al. [Phys. Rev. Lett. 84, 1716 (2000)].     

Migration of nitrogen in hexagonal Ge2Sb2Te5: An ab‐initio study

The migration barrier energies of the nitrogen atom and N₂ molecule, and the activation barriers for the dissociation and formation of N₂ in Ge₂Sb₂Te₅ were calculated by ab‐initio methods. Various transition and metastable states were found along the migration pathway. Migration barrier energies up to 1.19 eV for the nitrogen atom suggest that it is difficult for it to move from one site to any other site or diffuse out from Ge₂Sb₂Te₅ although doped nitrogen is energetically less stable with respect to N₂ in vacuum. N₂ in Ge₂Sb₂Te₅ was hardly expected to dissociate into nitrogen atoms and vice versa. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)