A Stable Dimer of SiS2 Arranged between Two Carbene Molecules

The Me‐cAAC:‐stabilized dimer of silicon disulfide (SiS₂) has been isolated in the molecular form as (Me‐cAAC:)₂Si₂S₄ ( 2 ) at room temperature [Me‐cAAC:=cyclic alkyl(amino) carbene]. Compound 2 has been synthesized from the reaction of (Me‐cAAC:)₂Si₂ with elemental sulfur in a 1:4 molar ratio under oxidative addition. This is the smallest molecular unit of silicon disulfide characterized by X‐ray crystallography, electron ionization mass spectrometry, and NMR spectroscopy. Structures with three sulfur atoms arranged around a silicon atom are known; however, 2 is the first structurally characterized silicon–sulfur compound containing one terminal and two bridging sulfur atoms at each silicon atom. Compound 2 shows no decomposition after storing for three months in an inert atmosphere at ambient temperature. The bonding of 2 has been further studied by theoretical calculations.     

A soluble molecular variant of the semiconducting silicondiselenide

Silicondiselenide is a semiconductor and exists as an insoluble polymer (SiSe₂)_n which is prepared by reacting elemental silicon with selenium powder in the temperature range of 400–850 °C. Herein, we report on the synthesis, isolation, and characterization of carbene stabilized molecular silicondiselenide in the form of (cAAC)₂Si₂Se₄ (3) [cAAC = cyclic alkyl(amino)carbene]. 3 is synthesized via reaction of diatomic silicon(0) compound (cAAC)₂Si₂ (2) with black selenium powder at –78 °C to room temperature. The intensely orange colored compound 3 is soluble in polar organic solvents and stable at room temperature for a month under an inert atmosphere. 3 decomposes above 245 °C. The molecular structure of 3 has been confirmed by X-ray single crystal diffraction. It is also characterized by UV-vis, IR, Raman spectroscopy and mass spectrometry. The stability, bonding, and electron density distributions of 3 have been studied by theoretical calculations.     

Self-assembly of a Mn9 nanoscopic mixed-valent cluster: synthesis, crystal structure, and magnetic behavior

A rare Mn9 micro3-oxo-centered mixed-valent cluster [Mn9O7(O2CPh)11(thmn)(py)2 (H2O)3] (1) is prepared by assembling an oxo-centered MnIIMnIII2 triangle, [Mn3O(O2CPh)6(py)2(H2O)].0.5MeCN, as the secondary building unit in the presence of a tripodal alcohol, 1,1,1-tris(hydroxymethyl)nitromethane (H3thmn), as the capping ligand. Complex 1 was formed along with a minor byproduct, [Mn6O2(O2CPh)10(MeCN)4] (2). Complex 1 was characterized by X-ray single-crystal structure analysis and was crystallized in a monoclinic system, space group P2(1)/n, a=16.214(6) A, b=25.874(10) A, c=26.497(10) A, and beta=94.214(7) degrees. The Manganese-oxo-carboxylate core in 1 looks like a funnel. Variable-temperature magnetic studies down to 2 K reveal the existence of dominant ferromagnetic interaction within the cluster. Alternating current susceptibility data of the cluster show strong frequency dependence of both the real and imaginary parts of susceptibility chi' and chi' below 5 K. Moreover, the calculated relaxation time, tau0=1.2x10(-7) s, and the energy barrier, DeltaE=25 K, are consistent with the single-molecule magnetic behavior of 1.     

A dispersed fluorescence and ab initio investigation of the X2B1 and A2A1 electronic states of the PH2 molecule

In this work, the X2B1 and A2A1 electronic states of the phosphino (PH2) free radical have been studied by dispersed fluorescence and ab initio methods. PH2 molecules were produced in a molecular free-jet apparatus by laser vaporizing a silicon rod in the presence of phosphine (PH3) gas diluted in helium. The laser-induced fluorescence, from the excited A2A1 electronic state down to the ground electronic state, was dispersed and analyzed. Ten (upsilon1upsilon2upsilon3) vibrationally excited levels of the ground electronic state, with upsilon1 < or = 2, upsilon2 < or = 6, and upsilon3 = 0, have been observed. Ab initio potential-energy surfaces for the X2B1 and A2A1 electronic states have been calculated at 210 points. These two states correlate with a 2Pi(u) state at linearity and they interact by the Renner-Teller coupling and spin-orbit coupling. Using the ab initio potential-energy surfaces with our RENNER computer program system, the vibronic structure and relative intensities of the A2A1 --> X2B1 emission band system have been calculated in order to corroborate the experimental assignments.     

A parallel interior point decomposition algorithm for block angular semidefinite programs

We present a two phase interior point decomposition framework for solving semidefinite (SDP) relaxations of sparse maxcut, stable set, and box constrained quadratic programs. In phase 1, we suitably modify the matrix completion scheme of Fukuda et al. (SIAM J. Optim. 11:647–674, 2000) to preprocess an existing SDP into an equivalent SDP in the block-angular form. In phase 2, we solve the resulting block-angular SDP using a regularized interior point decomposition algorithm, in an iterative fashion between a master problem (a quadratic program); and decomposed and distributed subproblems (smaller SDPs) in a parallel and distributed high performance computing environment. We compare our MPI (Message Passing Interface) implementation of the decomposition algorithm on the distributed Henry2 cluster with the OpenMP version of CSDP (Borchers and Young in Comput. Optim. Appl. 37:355–369, 2007) on the IBM Power5 shared memory system at NC State University. Our computational results indicate that the decomposition algorithm (a) solves large SDPs to 2–3 digits of accuracy where CSDP runs out of memory; (b) returns competitive solution times with the OpenMP version of CSDP, and (c) attains a good parallel scalability. Comparing our results with Fujisawa et al. (Optim. Methods Softw. 21:17–39, 2006), we also show that a suitable modification of the matrix completion scheme can be used in the solution of larger SDPs than was previously possible.     

Magnetic anomalies in CeIn(2)

The magnetic behavior of binary compound CeIn(2) has been reported to be unusual in the sense that this compound appears to exhibit a first-order ferromagnetic transition at a rather high temperature of (T(C)=)22 K, which is not so common for Ce systems. In order to throw more light on the magnetic behavior of this compound, we have carried out detailed magnetization, and electrical resistivity studies as a function of temperature, magnetic field and external pressure, in addition to heat-capacity measurements. The plots of H/M versus M(2) at low fields are interestingly characterized by negative slopes, not only near T(C), but also at lower temperatures, a source of which could be attributed to magnetic-field-induced transitions at much lower temperatures. The sign of magnetoresistance tends to change from positive to negative with increasing temperature, as though there is a gradual change in the magnetic character. Finally, the magnetic ordering temperature increases with increasing pressure (until 20 kbar), as though this compound lies at the left-hand side of the peak in Doniach’s magnetic phase diagram.     

Performance assessment of a new energy harvesting system using thermoelectric generator coupled with solar radiation on hybrid nanofluids

Journal of Thermal Analysis and Calorimetry - Combining energy recovery and renewable energy technologies for energy harvesting systems is a real challenge. In the present study, an innovative new...