Inhibition of premixed and nonpremixed flames with phosphorus-containing compounds

The inhibition/extinction of various flames—premixed stoichiometric C₃H₈/air, nonpremixed counterflow CH₄/O₂/N₂, and nonpremixed coflow n-heptane/air cup-burner flames doped with a number of phosphorus-containing compounds (PCCs)—has been investigated experimentally. More than 20 PCCs (organic phosphates, phosphonates, phosphates) and their fluorinated derivatives were studied. All PCCs exhibited similar dependencies in burning velocities, extinction strain rates, and extinction volume fractions of CO₂ upon PCC loading in the range of mole fractions of 0–7000 ppm within an experimental deviation of ± 5%. This confirms that the inhibition effectiveness of the PCCs is influenced by the phosphorus content in the PCC molecule rather than by the structure of the molecule. The burning velocity of a stoichiometric C₃H₈/air mixture and the extinction strain rate of a nonpremixed counterflow CH₄/O₂/N₂ flame doped with trimethylphosphate were calculated. Satisfactory agreement between experimental and modeling results confirms the conclusion that the reactions of phosphorus oxyacids with radicals are responsible for flame inhibition.     

基于拓扑结构的碱金属化合物摩尔磁化率的支持向量回归研究

基于经典电动力学导出的表征简单离子磁化率的磁性点价g_i所构建的分子磁性连接性指数?^mF及45种碱金属化合物的摩尔磁化率χ_m的实测数据集,利用粒子群寻优的支持向量回归（SVR）方法,建立了基于⁰F和¹F的碱金属化合物χ_m的预测模型,并与基于多元线性回归（MLR）模型的计算结果进行了比较.结果显示,基于9次交叉验证的SVR模型预测的平均绝对误差、平均相对误差绝对值以及均方根误差均比MLR模型小,表明SVR模型的回归预测能力优于MLR.研究表明,磁性连接性指数^mF是一种合适的分子描述符,SVR是一种预测碱金属化合物χ_m的有效方法. 关键词： 碱金属化合物 摩尔磁化率 支持向量回归 预测     

Unoccupied band dispersion of Si(1 1 1):√3 × √3-Ag surface studied by time- and angle-resolved two-photon photoemission spectroscopy

Band dispersion and transient population of unoccupied electronic states on Si(1 1 1):√3 × √3-Ag surface have been studied by time-resolved (TR) and angle-resolved (AR) two-photon photoemission (2PPE) spectroscopy. The band dispersions originating from unoccupied electronic states have been identified from the comparison between AR-2PPE spectra and angle-resolved one-photon photoemission spectra with synchrotron radiation. A lifetime of unoccupied surface state has been determined from the TR-2PPE spectra.     

In situ spectroelectrochemical surface-enhanced Raman scattering (SERS) investigations on composite Ag/TiO2-nanotubes/Ti substrates

A tubular array of TiO₂-nanotubes on a Ti substrate was used as a support for an Ag sputter-deposited layer intended for surface-enhanced Raman scattering (SERS) investigations. Composite samples of Ag/TiO₂-nanotube/Ti were studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Raman spectra of pyridine (as a probe molecule) were measured at different cathodic potentials ranging from −0.2 down to −1.2 V after the pyridine had been adsorbed on the TiO₂-nanotube/Ti substrates covered with the Ag deposit. In addition, SERS spectra on a bulk electrochemically-roughened Ag reference substrate, were also measured.The SERS activity of the composite samples was strongly dependent on the amount of Ag deposit and, in some cases, was even higher than that for the Ag reference substrate. The SERS intensity vs. electrode potential dependences measured were interpreted in terms of the modified electronic structure of the Ag deposits due to the interaction of the Ag clusters with the TiO₂-nanotube/Ti substrate.     

Spin-peierls transition in dimerized stacks of anion-radical salt (N-Me-2,5-di-Me-Pz)(TCNQ)2, (Pz is pyrazine)

An anion-radical salt (ARS) (N-Me-2,5-di-Me-Pz)(TCNQ)₂, where Pz is pyrazine, was synthesized and its crystal structure was resolved. X-ray diffraction experiments on single crystals were performed. Heat capacity was measured in the temperature range from 2 to 300 K. Magnetisation and magnetic susceptibility were measured in the temperature range from 2 to 300 K and the low-temperature part was measured in magnetic fields from 5 mT to 5 T. The experimental results were explained in terms of dimerized Heisenberg spin chain model. Numerical calculations were performed and compared with experimental data.     

Core-level photoemission of the Si(1 1 1)– -Ag surface using synchrotron radiation

The evolution of Si 2p core-level photoemission during a structural conversion from the Si (1 1 1)– -Ag to the Si(1 1 1)– -Ag superstructures induced by Ag adatoms adsorption at 140 K was studied using synchrotron radiation. The component from the top-layer Si-trimer atoms on the former surface was found to split into two components in the latter surface. The result is discussed in terms of a relaxation in some of the Si trimers induced by Ag adatoms sitting on the nearby Ag triangles of the -Ag substrate. The intensity ratio between the split components is a key to exclude some structure models proposed so far for the phases.     

Growth and electronic properties of ultra-thin Ag films on Ni(1 1 1)

We studied the growth mode and electronic properties of ultra-thin silver films deposited on Ni(1 1 1) surface by means of scanning tunnelling microscopy (STM) and angle resolved photoemission spectroscopy (ARPES). The formation of the 4d-quantum well states (QWS) was analysed within the phase accumulation model (PAM). The electronic structure of the 1 ML film is consistent with the silver layer which very weakly interacts with the supporting surface. The line-shape analysis of Ag-4d_xz,yz QWS spectrum support the notion of strong localization of these states within the silver layer. The asymmetry of the photoemission peaks implies that the decay of the photo-hole appears to be influenced by the dynamics of the electrons in the supporting surface.     

Electronic properties close to Dirac cone in two-dimensional organic conductor α-(BEDT-TTF)<Subscript>2</Subscript>I<Subscript>3</Subscript>

A zero-gap state (ZGS) has been found in a bulk system of two-dimensional organic conductor, α-(BEDT-TTF)₂I₃ salt which consists of four sites of donor molecules in a unit cell. In the present paper, the characteristic of the ZGS is analyzed in detail and the electronic properties are examined in the vicinity of the Dirac point where the conduction and valence bands degenerate to form the zero-gap. The eigenvectors of the energy band have four components of respective sites, where two of them correspond to inequivalent sites and the other two correspond to equivalent sites. It is shown that the former exhibits an exotic momentum dependence around the contact point and the latter shows almost a constant dependence. The density of states of each site close to the Dirac point is calculated to demonstrate the temperature dependence of the local magnetic susceptibility and the local nuclear magnetic relaxation rate. Further, the robust property of the ZGS against the anion potential is also shown by using the second-order perturbation.     

Conformations and enthalpies of formation of methylenecyclohexane, 1,4‐dimethylenecyclohexane,cyclohexanone, 4‐methylenecyclohexanone, 1,4‐cyclohexanedione,and their mono‐ and dioxa derivatives by G3(MP2)//B3LYP calculations

A computational study of the stable conformations and gas‐phase enthalpies of formation at 25 °C of the title compounds has been carried out by G3(MP2)//B3LYP calculations. The work stems from our early observations on the thermodynamic and NMR spectroscopic properties of 2‐methylenetetrahydropyran and related compounds suggesting a dominating chair conformation, with poor p–π overlap in the ? O? C?C moiety, for these compounds. Besides computational verification of the chair conformation of 2‐methylenetetrahydropyran, the work was extended to find out the stable conformations of a number of other related compounds and to evaluate the relative stabilities of the various conformers. Another important goal of the work was the estimation of the gas‐phase enthalpies of formation of the present compounds, for which such literature data are scarce. A significant error in the literature value of the enthalpy of formation of methylenecyclohexane was found. Finally, the relative enthalpy levels of the isomeric compounds of this work are discussed. The high thermodynamic stability of the compounds containing an ester functional group, ? O? C?O, relative to the stability of isomeric compounds with an ? O? C?C moiety in place of the ester function, is demonstrated. Copyright © 2009 John Wiley & Sons, Ltd.