Transmission of the spin-spin coupling constants through hydrogen bonds in ammonia clusters

Spin-spin coupling constants are reported using six ab initio and fifteen DFT methods for dimers and larger clusters of ammonia. An analysis of components (Fermi contact, spin dipole, paramagnetic spin-orbit, and diamagnetic spin-orbit) of more relevant coupling constants ¹J_NH′, ^1hJ_NH′ and ^2hJ_NN has been carried out. Fermi contact is the dominant term in the total value for all constants. For dimers, a relationship between the addition of direct and intermolecular coupling constants gives the direct constants of monomer. From the comparison of all ab initio and DFT methods for dimers, SOPPA(CCSD) and S55VWN5 methods are, respectively, more reliable taking into account their accuracy and the computing time. Both methods are employed for the analysis of the transmission of coupling constants through the hydrogen bond for ammonia clusters. A linear relation between the intermolecular constants ^1hJ_NH′ and the length of the hydrogen bond is found.     

Preparation of PdAu/C-Sb2O5·SnO2 electrocatalysts by borohydride reduction process for direct formic acid fuel cell

Pd/C-Sb₂O₅·SnO₂ and PdAu/C-Sb₂O₅·SnO₂ electrocatalysts with different PdAu atomic ratio (90:10, 70:30, and 50:50) were prepared by borohydride reduction method, and characterized by X-ray diffraction, transmission electron microscopy, cyclic voltammetry, chronoamperommetry, and performance test on direct formic acid fuel cell at 100 °C. X-ray diffraction showed for Pd/C-Sb₂O₅·SnO₂ the presence of Pd face-centered cubic (fcc) system, while for PdAu/C-Sb₂O₅·SnO₂ it showed the presence of Pd fcc phase, PdAu fcc alloys and a segregated phases fcc Pd-rich and Au-rich phases. TEM micrographs and histograms for all electrocatalysts showed that the nanoparticles where not well dispersed on the support and some agglomerates were present. The electrochemical studies showed that PdAu/C-Sb₂O₅·SnO₂ (70:30) had superior performance for formic acid electro-oxidation at 25 °C compared to others electrocatalysts prepared while PdAu/C-Sb₂O₅·SnO₂ (90:10) showed superior performance in direct formic acidic fuel cell at 100 °C. These results indicated that the addition of 10–30 % Au to Pd favor the electro-oxidation of formic acid. This effect could be attributed to the synergy between the constituents of the electrocatalyst (metallic Pd and Au, SnO₂, and Sb₂O₅·SnO₂).     

Quantitative simulation of photoacoustic signals using finite element modelling software

This paper aims to demonstrate the quantitative simulation of photoacoustic signals using finite element modelling software. The software Comsol Multiphysics is used to calculate the response of a differential Helmholtz resonator cell previously modeled using an electrical analogy. Quality factors and resonance frequencies are compared with experimental ones. Moreover, for the first time, the absorption coefficient of the gas sample and the laser intensity are also used to quantitatively predict photoacoustic signal that can be obtained in such a configuration.     

Compression of long-cavity Ti:sapphire oscillator pulses with large-mode-area photonic crystal fibers

Motivated by the pulse compression challenge of novel long-cavity, high-pulse-energy Ti:sapphire laser oscillators, we report on ~280 nm supercontinuum generation and 4.5-times compression of close to transform limited, high-energy oscillator pulses using different large-mode-area photonic crystal fibers and standard chirped mirrors. As input, we used pulses of a long-cavity Ti:sapphire oscillator with 190 nJ pulse energy, 70 fs pulse length and 3.6 MHz repetition rate. Compressed pulses at the fiber/compressor output had a duration of 15–18 fs with up to 100 nJ pulse energy representing as much as 53 % throughput for the fiber/chirped mirror system. Using transform-limited input pulses, we could use short fiber pieces and thus a simple, low-dispersion chirped mirror compressor comprised of one pair of mirrors.     

High-gain amplification in Yb:CaF2 crystals pumped by a high-brightness Yb-doped 976 nm fiber laser

We report on high single-pass gain in Yb:CaF₂ crystal longitudinally pumped with a 40 W high-brightness fiber laser source based on an ytterbium-doped ultra-large core photonic crystal rod-type fiber operating at 976 nm. A single-pass small-signal gain of 3.2 has been achieved in a 6 % Yb-doped 10-mm-long CaF₂ crystal at room temperature, outperforming any CW-diode-pumped scheme and paving the way towards very promising innovative lasers and amplifiers schemes merging the Yb-doped solid-state and fiber technologies.     

On Certain Kähler Quotients of Quaternionic Kähler Manifolds

We prove that, given a certain isometric action of a two-dimensional Abelian group A on a quaternionic Kähler manifold M which preserves a submanifold N ? M, the quotient M′ = N/A has a natural Kähler structure. We verify that the assumptions on the group action and on the submanifold N ? M are satisfied for a large class of examples obtained from the supergravity c-map. In particular, we find that all quaternionic Kähler manifolds M in the image of the c-map admit an integrable complex structure compatible with the quaternionic structure, such that N ? M is a complex submanifold. Finally, we discuss how the existence of the Kähler structure on M′ is required by the consistency of spontaneous ${\mathcal{N} = 2}$ to ${\mathcal{N} = 1}$ supersymmetry breaking.     

Time-Ordering and a Generalized Magnus Expansion

Both the classical time-ordering and the Magnus expansion are well known in the context of linear initial value problems. Motivated by the noncommutativity between time-ordering and time derivation, and related problems raised recently in statistical physics, we introduce a generalization of the Magnus expansion. Whereas the classical expansion computes the logarithm of the evolution operator of a linear differential equation, our generalization addresses the same problem, including, however, directly a non-trivial initial condition. As a by-product we recover a variant of the time-ordering operation, known as ${\mathsf{T}^\ast}$ -ordering. Eventually, placing our results in the general context of Rota–Baxter algebras permits us to present them in a more natural algebraic setting. It encompasses, for example, the case where one considers linear difference equations instead of linear differential equations.     

Electrochemical characterization of core@shell CoFe2O4/Au composite

Quantum dots (QDs) have received considerable attention due to their unique optical and electrical properties. Although substantial research has focused on the potential applications and toxicological impacts of QDs, far less effort has been directed toward understanding their fate and transport in the environment. In this work, the effect of four coatings, polyethylene glycol functionalized polymer (PEGP), carboxyl derivatized polymer (COOHP), linoleic acid (LA), and polyacrylic acid-octylamine (PAA-OA), on the transport and retention of QDs in porous media were evaluated under environmentally relevant conditions. Aqueous QD suspensions (ca. 10 nM) were introduced into water-saturated columns packed with 40–50 mesh Ottawa sand at a pore-water velocity of 7.6 m/day. At an ionic strength (IS) of 3 mM and pH of 7, PEGP-coated QDs were completely retained within the column, while more than 60 % of COOHP-coated QDs were transported through a column run under identical conditions. When PAA-OA and LA were used as coatings, effluent QD recoveries increased to more than 65 and 89 % of the injected mass, respectively. Additionally, a decrease in pH from 9.5 to 5.0, or an increase of IS from 0 to 30 mM reduced the eluted mass of PAA-OA-coated QDs by more than 2 and 15 times, respectively. The relative mobility of coated QDs (LA > PAA-OA > COOHP > PEGP) was consistent with total interaction energy profiles between QDs and sand surfaces calculated based on Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. At an IS of 3 mM (NaCl) and pH 7, a linear correlation was obtained between the fraction of eluted QDs and the magnitude of the primary interaction energy barrier. These findings demonstrate the strong dependence of QD transport on coating type and indicate that interaction energies based on DLVO theory can be used to predict the relative mobility of QDs in porous media.