Switching-on superparamagnetism in Mn/CdSe quantum dots

Mn ion doping of CdSe and other semimagnetic quantum dot (QDs) alloys has been an area of active speculation for over a decade. We report evidence of Mn(II) doping of CdSe grown from a cubic single source precursor that is superparamagnetic (SPM) with a blocking temperature of 40 K following thermal annealing. Prior to thermal annealing the 4 nm Mn/CdSe (1% Mn) QDs exhibit mainly paramagnetic behavior between 300 and 2 K, with a weak antiferromagnetic exchange. Following thermal annealing of the sample, high-temperature ferromagnetic exchange is observed in the magnetization data with the onset of an SPM phase at 40 K that exhibits a coercivity of 0.1 T at 2 K. The switching-on of SPM behavior is believed to be linked to ion migration with formation of (Se-Mn-Se-Mn-Se-Mn)n centers within the nanocrystal that exhibit coupled magnetic moments. Electron paramagnetic resonance (EPR) provides evidence of two distorted T(d) Mn core sites, a clustered site (dipolar broadened), and a localized Mn site (hyperfine-split). The ratio of the EPR signature for the dipolar broadened site increases following annealing and shows a hysteretic response around the blocking temperature. These observations suggest that thermal annealing results in enhanced cluster formation explaining the onset of the SPM phase in these nanoscale materials. Evidence of SPM behavior is evident in the field-dependent non-Langevin magnetization with a tangential loss in the ac-magnetic susceptibility and the Mydosh parameter (phi = 0.16).     

The properties of the [Mn12O12(O2CR)16(H2O)4] single-molecule magnets in truly axial symmetry: [Mn12O12(O2CCH2Br)16(H2O)4].4CH2Cl2

Detailed studies are reported of a Mn(12) single-molecule magnet (SMM) in truly axial (tetragonal) symmetry. The complex is [Mn(12)O(12)(O(2)CCH(2)Br)(16)(H(2)O)(4)].4CH(2)Cl(2) (2.4CH(2)Cl(2) or Mn(12)-BrAc), obtained by the standard carboxylate substitution method. The complex has an S = 10 ground state, typical of the Mn(12) family, and displays frequency-dependent out-of-phase AC susceptibility signals and hysteresis in single-crystal magnetization vs applied DC field sweeps. Single-crystal high-frequency EPR spectra in frequencies up to 360 GHz exhibit narrow signals that are not overlapping multiplets, in contrast to [Mn(12)O(12)(O(2)CMe)(16)(H(2)O)(4)].2MeCO(2)H.4H(2)O (1 or Mn(12)-Ac), which also crystallizes in an axial (tetragonal) space group but which now is recognized to consist of a mixture of six hydrogen-bonded isomers in the crystal and thus gives multiple, inhomogeneously broadened EPR signals. Similarly, single-crystal (55)Mn NMR spectra on Mn(12)-BrAc display much sharper signals than a single crystal of Mn(12)-Ac, and this allows one Mn(III) signal to show an almost baseline-resolved quintet from quadrupolar splitting ((55)Mn, I = 5/2, 100%), allowing quadrupole coupling parameters (e(2)qQ) to be determined. In addition, it was found that crushing crystals of Mn(12)-BrAc into a microcrystalline powder causes severe broadening and shifts of the NMR resonances, emphasizing the superiority of single-crystal studies. The combined results establish that Mn(12)-BrAc is far superior to Mn(12)-Ac for the study of the intrinsic properties of the Mn(12) family of SMMs in axial symmetry, and for the search for new phenomena such as quantum interference effects caused by higher-order (>2nd-order) transverse terms in the spin Hamiltonian.     

Growth and properties of microcrystalline germanium–carbide alloys grown using electron cyclotron resonance plasma processing

We report on the growth and properties of a new material, microcrystalline (Ge, C), which has potentially important optical, electrical and structural properties. The material was grown using a remote, low pressure electron cyclotron resosnance (ECR) plasma process on glass, stainless steel and c-Si substrates. The growth was done with hydrogen dilution and ion bombardment at temperatures of 350–400°C. We discovered that the optical absorption curve parallels that of c-Ge, with increased bandgaps as C is incorporated. We obtained up to 2% C incorporation, which increased the gap to 1.1 eV. At comparable bandgaps, the absorption coefficient of the (Ge, C) material is much larger than that of c-Si. Raman and X-ray measurements detected microcrystalline structure, and a dependence of grain size on the substrate used. The lattice constant contracted with C incorporation, approximately obeying Vegard’s law. Both undoped and n-doped materials were grown.     

Synthesis and photovoltaic properties of a furan-diketopyrrolopyrrole-fluorene terpolymer

We report the synthesis of two solution-processable reduced band gap donor–acceptor conjugated polymers p(C8-DPP-F) and p(C12-DPP-F), composed from 9,9-dioctylfluorene as the donor moiety, diketopyrrolopyrrole (DPP) moiety as the acceptor moiety and furan bridges. Two different alkyl chains, n-dodecyl and n-octyl were used on the DPP moiety and the impact of this structural modification evaluated in detail. Both polymers exhibited similar optical and electrochemical properties with optical band gap of around 1.75 eV as result of LUMO levels near −3.4 eV and high-lying HOMO levels of ∼5.2 eV. Bulk heterojunction photovoltaic devices using these polymers electron donors along with PC₇₀BM as the electron acceptor, gave power conversion efficiency of 1.60% and 0.75% for p(C12-DPP-F) and p(C8-DPP-F) respectively.     

Correction to: Chronology and characteristics of groundwater along the United Arab Emirates-Oman arid region: a guide for regional sustainability

Journal of Radioanalytical and Nuclear Chemistry - In the original publication of the article, the eighth author’s name and Figure 1 were published incorrectly.     

A class of higher order compact schemes for the unsteady two‐dimensional convection–diffusion equation with variable convection coefficients

A class of higher order compact (HOC) schemes has been developed with weighted time discretization for the two‐dimensional unsteady convection–diffusion equation with variable convection coefficients. The schemes are second or lower order accurate in time depending on the choice of the weighted average parameter μ and fourth order accurate in space. For 0.5?μ?1, the schemes are unconditionally stable. Unlike usual HOC schemes, these schemes are capable of using a grid aspect ratio other than unity. They efficiently capture both transient and steady solutions of linear and nonlinear convection–diffusion equations with Dirichlet as well as Neumann boundary condition. They are applied to one linear convection–diffusion problem and three flows of varying complexities governed by the two‐dimensional incompressible Navier–Stokes equations. Results obtained are in excellent agreement with analytical and established numerical results. Overall the schemes are found to be robust, efficient and accurate. Copyright © 2002 John Wiley & Sons, Ltd.     

Hydrogen-bonded ferroelectrics: Evidence for Slater configurations from E.P.R. studies of X-irradiated KH2AsO4 and NH4H2AsO4

The temperature dependence of the powder E.P.R. spectrum of the AsO₄ ^4- centre in x-irradiated samples of KH₂AsO₄ and NH₄H₂AsO₄ yields results which can be understood as arising from exchange processes taking place between the six configurations in the Slater model for this type of hydrogen-bonded ferroelectric and antiferroelectric. Knowing that the ⁷⁵As hyperfine parameters have rhombic symmetry in the compounds studied, it is possible to interpret certain specific features in the spectra as being associated with the Slater configurations of higher energy.     

Growth of barium oxalate crystals in agar–agar gel and their characterization

Single crystals of barium oxalate have been grown by gel method using agar‐agar gel as media of growth at ambient temperature. The optimum conditions were established by varying various parameters such as concentration of gel, concentration of reactant, gel setting time etc. Prismatic platy shaped transparent crystals were obtained. The grown crystals were characterized through powder X‐ray diffraction (XRD), Fourier transform infrared (FT‐IR) studies, Thermogravimetric (TGA) and Differential thermal analysis (DTA). The compound crystallizes under monoclinic structure with lattice parameters a = 6.6562 Å, b = 8.0464 Å, c = 2.8090 Å, β= 96.832°, and V = 149.38 ų. The FT‐IR spectrum indicates OH and carbonyl group along with the presence of metal‐oxygen bond. The TGA indicates 17.75% weight loss at 550°C from which the decomposition pattern is formulated. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)