Integrated absorption of a spectral line with the Voigt profile

A simple approximation has been found for the integrated absorpton of a spectral line with Voigt profile. It is expressed in terms of the integrated absorption of the Doppler and Lorentz profiles. The maximum error is 8%.     

Subnanosecond multiphonon relaxation of divalent copper impurities in LiTaO3

The temperature dependence of the lifetime of the excited ²T₂ state of the Cu²⁺ ion in a LiTaO₃ crystalline host has been measured with picosecond optical pulses. Its value ranges from 450 psec at 22°K to 10 psec at 423°K. Consistent with this result is the observation of weak fluorescence at 1.75 μm having a low temperature quantum efficiency of ～ 10^?6. The experimental results are in reasonably good agreement with recent theoretical models based on strong coupling of the Cu²⁺ impurities to the host lattice.     

Pressure-induced intermetallic valence transition in BiNiO3

The valence state change of BiNiO3 perovskite under pressure has been investigated by a powder neutron diffraction study and electronic-state calculations. At ambient pressure, BiNiO3 has the unusual charge distribution Bi(3+)(0.5)Bi(5+)(0.5)Ni(2+)O3 with ordering of Bi(3+) and Bi(5+)charges on the A sites of a highly distorted perovskite structure. High-pressure neutron diffraction measurements and bond valence sum calculations show that the pressure-induced melting of the charge disproportionated state leads to a simultaneous charge transfer from Ni to Bi, so that the high-pressure phase is metallic Bi(3+)Ni(3+)O3. This unprecedented charge transfer between A and B site cations coupled to electronic instabilities at both sites leads to a variety of ground states, and it is predicted that a Ni-charge disproportionated state should also be observable.     

Synthesis and Structure Elucidation of 8-Methyl- and 9-Methyl-exo-2-carbomethoxy-endo-tricyclo[5.2.1.02,6]deca-3,8-dien-5-ones

A mixture of 1-methyl- and 2-methyl-1,4,4a,8a,-tetrahydro-endo-1,4-methano-naphthalene-5,8-diones ( 2 & 3 ) was chemically transformed into separable methyl substituted tricyclo[5.2.1.0^2,6]decadienones 7 , 8 & 9 . The structure of 8 & 9 were elucidated via Cope rearrangement of their corresponding allylic alcohols ( 10 & 11 ) to furnish 12 & 13 respectively.     

Complex scale-free networks with tunable power-law exponent and clustering

We introduce a network evolution process motivated by the network of citations in the scientific literature. In each iteration of the process a node is born and directed links are created from the new node to a set of target nodes already in the network. This set includes m$m$ “ambassador” nodes and l$l$ of each ambassador’s descendants where m$m$ and l$l$ are random variables selected from any choice of distributions _pl$p_l$ and _qm$q_m$. The process mimics the tendency of authors to cite varying numbers of papers included in the bibliographies of the other papers they cite. We show that the degree distributions of the networks generated after a large number of iterations are scale-free and derive an expression for the power-law exponent. In a particular case of the model where the number of ambassadors is always the constant m$m$ and the number of selected descendants from each ambassador is the constant l$l$, the power-law exponent is (2l+1)/l$(2l+1)/l$. For this example we derive expressions for the degree distribution and clustering coefficient in terms of l$l$ and m$m$. We conclude that the proposed model can be tuned to have the same power law exponent and clustering coefficient of a broad range of the scale-free distributions that have been studied empirically.     

Transport properties of composite membranes containing silicon dioxide and Nafion

Silicon dioxide (SiO₂) nanoparticles were incorporated into Nafion 115 membranes using the sol–gel method in order to investigate their effect on water retention/transport, proton concentration, effective proton mobility, and proton conductivity. By adjusting the sol–gel reaction time, Nafion/SiO₂ membranes were fabricated with SiO₂ content ranging from 5.9 to 33.3 wt%. Because the density of the membranes decreased with increasing SiO₂ content and because dimensional changes with swelling in water of the composite membranes were less than that of unmodified Nafion 115 despite having increased water content, the theory that rigid scaffolding is formed inside the membrane is supported. Water content increases with increasing SiO₂ content due to void space formed inside the membrane. This increase in water content dilutes the protons in the membrane leading to lower proton concentration and therefore lower proton conductivity. A decreasing effective proton mobility with increasing SiO₂ content, likely due to an increase in the tortuosity of the proton-conducting pathway, also contributes to the decreasing conductivity. However, as evidenced by the similar water vapour permeance values, the SiO₂ nanoparticles do not increase the effective tortuosity of the water vapour transmission pathways.     

Dipole effects on cation-pi interactions: absolute bond dissociation energies of complexes of alkali metal cations to N-methylaniline and N,N-dimethylaniline

Threshold collision-induced dissociation of M (+)( nMA) x with Xe is studied using guided ion beam mass spectrometry, where nMA = N-methylaniline and N, N-dimethylaniline and x = 1 and 2. M (+) includes the following alkali metal cations: Li (+), Na (+), K (+), Rb (+), and Cs (+). In all cases, the primary dissociation pathway corresponds to the endothermic loss of an intact nMA ligand. The primary cross section thresholds are interpreted to yield 0 and 298 K bond dissociation energies (BDEs) for ( nMA) x-1 M (+)-( nMA) after accounting for the effects of multiple ion-neutral collisions, the internal and kinetic energy distributions of the reactants, and the dissociation lifetimes. Density functional theory calculations at the B3LYP/6-31G* level of theory are used to determine the structures of these complexes, which are also used in single-point calculations at the MP2(full)/6-311+G(2d,2p) level to determine theoretical BDEs. The results of these studies are compared to previous studies of the analogous M (+)(aniline) x complexes to examine the effects of methylation of the amino group on the binding interactions. Comparisons are also made to a wide variety of cation-pi complexes previously studied to elucidate the contributions that ion-dipole, ion-induced-dipole, and ion-quadrupole interactions make to the overall binding.     

Laser beam combining and cleanup by stimulated Brillouin scattering in a multimode optical fiber

A new technique for combining low-power laser beams has been demonstrated by use of semiconductor diode lasers. The technique, which is appropriate for any single-longitudinal-mode laser, is based on stimulated Brillouin scattering (SBS) in long multimode optical fibers. It produces a clean Gaussian-like beam that corresponds to the fundamental fiber mode, irrespective of the profile of the pump. Coherent as well as incoherent combining was demonstrated, and conversion slope efficiencies as high as 67% and 83% were shown to be achievable for the single-pass and ring-cavity SBS geometries, respectively.