Experimental and molecular modeling investigation of (E)-N-{2-[(2-hydroxybenzylidene)amino]phenyl}benzenesulfonamide

The Schiff base compound (E)-N-{2-[(2-hydroxybenzylidene)amino]phenyl}benzenesulfonamide has been synthesized and characterized by IR, NMR and Uv-vis spectroscopies, and single-crystal X-ray diffraction technique. In addition, quantum chemical calculations employing density functional theory (DFT) method with the 6–311++G(d,p) basis set were performed to study the molecular, spectroscopic and some electronic structure properties of the title compound, and the results were compared with the experimental findings. There exists a good correlation between experimental and theoretical data. Enol-imine/keto-amine tautomerization mechanism was investigated in the gas phase and in solution phase using the polarizable continuum model (PCM) approximation. The energetic and thermodynamic parameters of the enol-imine?→?keto-amine transfer process show that the single proton exchange is thermodynamically unfavored both in the gas phase and in solution phase. However, the reverse reaction seems to be feasible with a low barrier height and is supported by negative values in enthalpy and free energy changes both in the gas phase and in solution phase. The solvent effect is found to be sizable with increasing polarity of the solvents for the reverse reaction. The predicted nonlinear optical properties of the compound are found to be much greater than those of urea.     

Nuclear quantum effects in liquid water from path-integral simulations using an ab initio force-matching approach

We have applied path integral simulations, in combination with new ab initio based water potentials, to investigate nuclear quantum effects in liquid water. Because direct ab initio path integral simulations are computationally expensive, a flexible water model is parameterised by force-matching to density functional theory-based molecular dynamics simulations. Static and dynamic properties of liquid water at ambient conditions are presented and the role of nuclear quantum effects, exchange-correlation functionals and dispersion corrections are discussed in regards to reproducing the experimental properties of liquid water.     

Precursor state of skyrmions in MnSi: a heat capacity study

The magnetic phase diagram of MnSi based on the detailed magneto‐heat capacity study is presented. It shows the A‐phase, a precursor to the formation of stable skyrmion lattice, along with the intermediate, helical, conical, ferromagnetic and paramagnetic phases. The field isotherms of specific heat in and around the transition temperature reveal the different magnetic modulations. The local minima represent the relatively low entropy state due to the formation of A‐phase as a precursor to the stable skyrmion lattice. The field‐induced second‐order phase transition is observed by melting the intermediate phase. The region of existence of first‐order phase transition is found to be, effectively, from helical to the intermediate phase. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spin-polarised DFT study of cobalt-doped gallium clusters

The structural, electronic and magnetic properties of small gallium clusters doped with Cobalt have been studied using spin-polarised density functional theory. The binding energy per atom, second-order differences of total energies and fragmentation energies of equilibrium geometries of the host Ga_n+1 and doped Ga_nCo (n = 1–12) clusters are computed. Doped clusters are found to be more stable than pure Ga clusters; Ga₃Co, Ga₅Co and Ga₈Co clusters are exceptionally stable. Doping with Co changes the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO–LUMO) gap, and also affects the magnetic moments of clusters.     

Variation of the electronic properties of zigzag boron nitride nanotubes by Al-doping: a DFT study

Boron nitride nanotubes (BNNTs) are semiconductors with a wide band gap. In comparison with carbon nanotubes (CNTs), BNNTs have higher chemical stability, excellent mechanical properties and higher thermal conductivity. In this paper, we study the effect of diameters and substituting B and N atoms of various zigzag BNNTs with Al, on structural and electronic properties of BNNTs in solid state using the density functional theory method. The results of calculations of density of states and band structure (band) showed that the band gap between the valence and conduction level increases as a result of the enhancement of tube diameter of BNNTs. Finally, the results showed that the electronic properties of the pristine BNNTs can be improved by doping Al atom in the zigzag configuration of tubes.     

Photothermally Induced Bistability of Emission of Yb-doped Ca4NdO(BO3)3 Single Crystals

We report on studies of changes in the emission spectra (excited at 808 nm) of the Yb-doped Ca₄NdO(BO₃)₃ single crystals due to the photothermal effects caused by the pulsed Nd:YAG laser. Increase of the sample's surface temperature after laser treatment leads to significant enhancement of the 1040 to 1060 nm emission (ascribed to the Nd^{3+ 4}F_3/2 → ⁴I_9/2, ⁴I_11/2 transitions) and simultaneous decrease of the 975 to 1050 nm emission (corresponding to the Yb^{3+ 2}F_5/2 → ²F_7/2 transition). We explain such an increase of the Nd³⁺ luminescence by thermally activated Yb³⁺ → Nd³⁺ energy transfer.     

周期性纳米洞内边缘氧饱和石墨烯纳米带的电子特性

利用基于密度泛函理论的第一性原理方法,研究了内边缘氧饱和的周期性凿洞石墨烯纳米带（G NR）的电子特性. 研究结果表明：对于凿洞锯齿形石墨烯纳米带（ZGNRs）,在非磁性态时不仅始终为金属,且金属性明显增强;反铁磁态（AFM）时为半导体的ZGNR,凿洞后可能成为金属;但铁磁态（FM）为金属的ZGNR,凿洞后一般变为半导体或半金属. 而对于凿洞的扶手椅形石墨烯（AGNRs）,其带隙会明显增加. 深入分析发现：这是由于氧原子对石墨烯纳米带边的电子特性有重要的影响,以及颈次级纳米带（NSNR）及边缘次级纳米带（ESNR）的不同宽度及边缘形状（锯齿或扶手椅形）能呈现出不同的量子限域效应. 这些研究对于发展纳米电子器件有重要的意义. 关键词： 石墨烯纳米带 纳米洞 内边缘氧饱和 电子特性     

Dynamic mechanical and morphological studies of homopolymer/block copolymer blends

A triblock copolymer of styrene-butadiene-styrene (SBS) was blended with a high and a low molecular weight polybutadiene [designated as PB(H) and PB(L), respectively]. Electron micrographs of these blends show that PB(L) was solubilized into the butadiene domains of the SBS, while PB(H) was present in a separate phase. Dynamic mechanical data of the SBS&PB(L) blends indicate the presence of an intermediate loss peak between those of the glass transitions of the styrene and butadiene blocks in SBS, which can be attributed to the slippage of untrapped entanglements of PB(L) chains. Similar data for blends containing PB(H) also show an intermediate loss peak, which is, however, due to crystallization and melting of the polycisbutadiene chains. The peak due to the primary glass transition of the butadiene phase was shifted to lower temperatures upon incorporation of PB(L) as a result of plasticization effect of PB(L). The same transition for PB(H) blends is split into a doublet because of the presence of the homopolymer in a separate phase. Dynamic mechanical data for cross-linked blends were also taken for comparison.