Theoretical studies of the tunneling splitting of malonaldehyde using the multiconfiguration time-dependent Hartree approach

Full dimensional multi-configuration time-dependent Hartree calculations of the zero point energy and the tunneling splitting of malonaldehyde using a recently published potential energy surface [Y. Wang, B. J. Braams, J. M. Bowman, S. Carter, and D. P. Tew, J. Chem. Phys. 128, 224314 (2008)] are reported. The potential energy surface has been approximated by a modified version of the n-mode representation and careful convergence check has been performed to ensure accurate results. The obtained value for the splitting (23.4 cm(-1)) is in acceptable agreement with the experimental value of 21.583 cm(-1). The computed zero-point-energy is 14,670 cm(-1) which is lower than previous results of Wang et al., but likely to be about 4 cm(-1) too low because of shortcomings of the n-mode representation of the potential. The energies reported in this abstract contain a correction to account for neglected vibrational angular momentum terms.     

Debundling, selection and release of SWNTs using fluorene-based photocleavable polymers

Photocleavable polymers based on 9,9-dialkylfluorene backbone and o-nitrobenzylether were designed and synthesized to obtain stable (n,m) enriched suspensions of semiconducting SWNTs in toluene. Photoirradiation of the suspensions triggered the precipitation of the SWNTs and TEM images indicate close packing of SWNTs pointing at partial removal of the coating polymer.     

Kinetics of iron–copper sulphides oxidation in relation to protohistoric copper smelting

This article deals with one specific step of the copper extractive metallurgy process: the roasting of iron–copper sulphides. It aims at shedding light on an archaeological issue: the reconstruction of the copper extractive metallurgy processes during protohistory (IV^e–II^e millennium BC). Experimental simulations are performed at laboratory scale by modelizing the conditions of protohistoric furnaces. Kinetic of roasting is studied by thermogravimetry combined with the physico-chemical analysis of synthetic products. The influence of two parameters is studied: (i) the temperature (773, 973 and 1173 K) and (ii) the granularity of the roasted ores (1 mm and 100 μm). In each case, the chemical mechanism governing the oxidation of iron copper sulphide is proposed. Apart from one extreme case (∅ = 1 mm; T = 773 K), it is showed that kinetic is controlled by the transport of molecular oxygen (O₂) from the gas to the grain surface. Moreover, we prove that, in some cases where the diffusivity of gaseous oxygen is low, roasting can be accelerated by the presence of an oxide, which constitute an in-situ source of oxygen. Theses experiments support the hypothesis that such a technique could have allowed a roasting process where iron and sulfur were removed by the solid oxygen instead of the gaseous oxygen. These results allow to validate a one-step copper smelting process starting from sulphidic ores, and to identify the experimental parameters of this process.     

Detection of pentatetraene by reaction of the ethynyl radical (C2H) with allene (CH2=C=CH2) at room temperature

The reaction of ethynyl radical (C(2)H) with allene (C(3)H(4)) at room temperature is investigated using an improved synchrotron multiplexed photoionization mass spectrometer (MPIMS) coupled to tunable vacuum ultraviolet (VUV) synchrotron radiation from the Advanced Light Source at the Lawrence Berkeley National Laboratory (LBNL). The orthogonal-accelerated time-of-flight mass spectrometer (OA-TOF) compared to the magnetic sector mass spectrometer used in a previous investigation of the title reaction (Phys. Chem. Chem. Phys., 2007, 9, 4291) enables more sensitive and selective detection of low-yield isomeric products. The C(5)H(4) isomer with the lowest ionization energy, pentatetraene, is now identified as a product of the reaction. Pentatetraene is predicted to be formed based on recent ab initio/RRKM calculations (Phys. Chem. Chem. Phys., 2010, 12, 2606) on the C(5)H(5) potential energy surface. However, the computed branching fraction for pentatetraene is predicted to be five times higher than that for methyldiacetylene, whereas experimentally the branching fraction of pentatetraene is observed to be small compared to that of methyldiacetylene. Although H-atom assisted isomerization of the products can affect isomer distribution measurements, isomerization has a negligible effect in this case. The kinetic behavior of the several C(5)H(4) isomers is identical, as obtained by time-dependent photoionization spectra. Even for high allene concentrations (and hence higher H-atom concentrations) no decay of the pentatetraene fraction is observed, indicating that H-assisted isomerization of pentatetraene to methyldiacetylene does not account for the difference between the experimental data and the theoretical branching ratios.     

Peroxy radical isomerization in the oxidation of isoprene

We report experimental evidence for the formation of C(5)-hydroperoxyaldehydes (HPALDs) from 1,6-H-shift isomerizations in peroxy radicals formed from the hydroxyl radical (OH) oxidation of 2-methyl-1,3-butadiene (isoprene). At 295 K, the isomerization rate of isoprene peroxy radicals (ISO2?) relative to the rate of reaction of ISO2? + HO2 is k(isom)(295)/(k(ISO2?+HO2)(295)) = (1.2 ± 0.6) x 10(8) mol cm(-3), or k(isom)(295) ? 0.002 s(-1). The temperature dependence of this rate was determined through experiments conducted at 295, 310 and 318 K and is well described by k(isom)(T)/(k(ISO2?+HO2)(T)) = 2.0 x 10(21) exp(-9000/T) mol cm(-3). The overall uncertainty in the isomerization rate (relative to k(ISO2?+HO2)) is estimated to be 50%. Peroxy radicals from the oxidation of the fully deuterated isoprene analog isomerize at a rate ～15 times slower than non-deuterated isoprene. The fraction of isoprene peroxy radicals reacting by 1,6-H-shift isomerization is estimated to be 8-11% globally, with values up to 20% in tropical regions.     

Numerical modeling of guided wave interaction with non-axisymmetric cracks in elastic cylinders

A three dimensional (3D) hybrid method combining the classical finite element (FE) method with the semi-analytical finite element (SAFE) technique is developed. This hybrid method is employed to study the interaction of guided waves with non-axisymmetric damages in cylinders. The near field surrounding the damage is analysed with the 3D FE method. The solution is expanded into sums of guided modes on both inlet and outlet cross-sections. Such eigenmode expansions enable separation into ingoing and outgoing waves, i.e., incident, reflected and transmitted waves. Using the SAFE method, elastic guided modes are then computed at the aforementioned cross-sections thus reducing the analysis to two dimensions (2D). The amplitudes of the incident modes are imposed, whereas those of the scattered modes are determined by solving the global system of the 3D hybrid FE-SAFE model. In this paper, a formula is proposed for the calculation of eigenforces and modal power flows from eigendisplacements and SAFE matrices. This has the advantage of simplifying the post-process of load eigenvectors in hybrid FE-SAFE methods. Results obtained for a vertical free-end cylinder are in good agreement with those published in the literature. Moreover, first results of the interaction of the fundamental compressional, flexural and torsional Pochhammer–Chree modes with non-axisymmetric vertical cracks are obtained and discussed. Then, the interactions of the fundamental compressional mode with oblique free-ends and cracks are briefly addressed. The power balance is shown to be satisfied with a good accuracy.     

Delicious not siliceous: expanded carbohydrates as renewable separation media for column chromatography

Expansion of native corn starch produces a high surface area mesoporous material capable of acting as a novel stationary phase for separating various mixtures of compounds.