Mass-analyzed threshold ionization spectroscopy of deuterium-substituted isotopomers of o-fluoroaniline and m-fluoroaniline cations

We applied the resonant two-photon ionization and mass-analyzed threshold ionization techniques to record the vibronic and cation spectra of deuterium-substituted isotopomers of o-fluoroaniline (OFA) and m-fluoroaniline (MFA). The origins of the S₁ ← S₀ electronic transitions and adiabatic ionization energies of these isotopomers were precisely determined.     

Wind identification along a flight trajectory,part 3: 2D-dynamic approach

This paper deals with the identification of the wind profile along a flight trajectory by means of a two-dimensional dynamic approach. In this approach, the wind velocity components are computed as the difference between the inertial velocity components and the airspeed components. The airspeed profile as well as the nominal thrust, drag, and lift profiles are obtained from the available DFDR measurements. The actual values of the thrust, drag, and lift are assumed to be proportional to the respective nominal values via multiplicative parameters, called the thrust, drag, and lift factors. The thrust, drag, and lift factors plus the inertial velocity components at impact are determined by matching the flight trajectory computed from DFDR data with the flight trajectory available from ATCR data. This leads to a least-square problem which is solved analytically under the additional requirement of closeness of the multiplicative factors to unity. Application of the 2D-dynamic approach to the case of Flight Delta 191 shows that, with reference to the last 180 sec before impact, the values of the multiplicative factors were 1.09, 0.84, and 0.89; this implies that the actual values of the thrust, drag, and lift were 9% above, 16% below, and 11% below their respective nominal values. For the last 60 sec before impact, the aircraft was subject to severe windshear, characterized by a horizontal wind velocity difference of 123 fps and a vertical wind velocity difference of 80 fps. The 2D-dynamic approach is applicable to the analysis of windshear accidents in take-off or landing, especially for the case of older-generation, shorter-range aircraft which do not carry the extensive instrumentation of newer-generation, longer-range aircraft. The same methodology can be extended to the investigation of aircraft accidents originating from causes other than windshear (e.g., icing, incorrect flap position, engine malfunction), above all if its precision is further increased by combining the 2D-dynamic approach and the 2D-kinematic approach.     

Effect of concentration of Er3+ ions on ultra-large index of refraction via atomic coherence in Er3+: YAG crystal

A four-level system is proposed to produce large index of refraction accompanied by vanishing absorption in the Er^{3+}-doped yttrium aluminium garnet (YAG) crystal. It is found that the high index of refraction with zero absorption can be provided by adjusting the incoherent pumping, the coherent field, as well as the concentration of Er^{3+} ions in the crystal. Furthermore, the value of the incoherent pump to achieve the high index of refraction with zero absorption is greatly changed with increasing the concentration of Er^{3+} ions in the crystal. This indicates that the effect of concentration on the high index of refraction with zero absorption cannot be neglected.     

Photostability of amino acids: internal conversion versus dissociation

Photodissociation dynamics for various tryptophan chromophores was studied at 193 or 248 nm using multimass ion imaging techniques. The competition between internal conversion to the ground electronic state and dissociation from the repulsive excited state reveals size-dependent photostability for these amino acid chromophores. As the size of chromophore increases, internal conversion to the ground state becomes the major nonradiative process. For tryptophan and larger chromophores, dissociation directly from the repulsive state is completely quenched.     

Unusual one-dimensional branched-chain structures assembled by a novel imidazole-containing tripodal ligand with cadmium(II) salts and their fluorescent property

Three novel coordination polymers [Cd₃(L)₂(μ-Br)(μ-Cl)Br₃Cl] (1), [Cd₃(L)₂(μ-Cl)₂Cl₄] (2) and [Cd(L)Cl]₂[CdCl₄]·H₂O (3) were obtained by reactions of an imidazole-containing tripodal ligand N¹-(2-aminoethyl)-N¹-(2-imidazolethyl)-ethane-1,2-diamine (L) with Cd(II) salts. Their structures were determined by X-ray crystallography. Crystal data for 1, monoclinic system, P2₁/c, a=7.752(4) Å, b=31.70(2) Å, c=14.012(7) Å, β=109.439(7)°, V=3247(3) Å³, Z=4. 2, monoclinic system, P2₁/c, a=7.6564(15) Å, b=31.433(6) Å, c=13.925(3) Å, β=109.89(3)°, V=3151.1(11) Å³, Z=4. 3, orthorhombic system, Pbcn, a=22.950(2) Å, b=8.435(7) Å, c=17.360(2) Å, V=3360.3(51) Å³, Z=4. Complexes 1 and 2 have similar one-dimensional (1D) branched-chain structure while complex 3 features a 1D zigzag cationic chain with [CdCl₄]²⁻ serving as counter anion. The photoluminescent measurements reveal that all the complexes exhibit blue fluorescence at room temperature in the solid state.     

Computational study of reaction pathways for the formation of indium nitride from trimethylindium with HN3: comparison of the reaction with NH3 and that on TiO2 rutile (110) surface

The reactions of trimethylindium (TMIn) with HN3 and NH3 are relevant to the chemical vapor deposition of indium nitride thin film. The mechanisms and energetics of these reactions in the gas phase have been investigated by density functional theory and ab initio calculations using the CCSD(T)/Lanl2dz//B3LYP/Lanl2dz and CCSD(T)/Lanl2dz//MP2/Lanl2dz methods. The results of both methods are in good agreement for the optimized geometries and relative energies. These results suggest that the reaction with HN3 forms a new stable product, dimethylindiumnitride, CH3-In=N-CH3 via another stable In(CH3)2N3 (dimethylindium azide, DMInA) intermediate. DMInA may undergo unimolecular decomposition to form CH3InNCH3 by two main possible pathways: (1) a stepwise decomposition process through N2 elimination followed by CH3 migration from In to the remaining N atom and (2) a concerted process involving the concurrent CH3 migration and N2 elimination directly giving N2+CH3InNCH3. The reaction of TMIn with NH3 forms a most stable product DMInNH2 following the initial association and CH4-elimination reaction. The required energy barrier for the elimination of the second CH4 molecule from DMInNH2 is 74.2 kcal/mol. Using these reactions, we predict the heats of formation at 0 K for all the products and finally for InN which is 123+/-1 kcal/mol predicted by the two methods. The gas-phase reaction of HN3 with TMIn is compared with that occurring on rutile TiO2 (110). The most noticeable difference is the high endothermicity of the gas-phase reaction for InN production (53 kcal/mol) and the contrasting large exothermicity (195 kcal/mol) released by the low-barrier Langmuir-Hinshelwood type processes following the adsorption of TMIn and HN3 on the surface producing a horizontally adsorbed InN(a), Ti-NIn-O(a), and other products, CH4(g)+N2(g)+2CH3O(a) [J. Phys. Chem. B 2006, 110, 2263].     

石墨炉-原子吸收光谱法测定某冶炼厂周边土壤、粮食、蔬菜中的镉

采集了某冶炼厂周围五个自然村(组)的31个土壤样品、5种粮食类样品、22种蔬菜类样品,以湿法-高压密闭消解法对样品进行前处理,并用石墨炉原子吸收光谱法测定了各样品中镉元素的含量,以研究该地区镉元素的分布情况.样品消解试剂为HNO3-HF-HClO4体系,石墨炉灰化温度为500℃,原子化温度为1800℃.测得土壤、粮食类、蔬菜类中镉的总平均含量分别为0.89、0.37、0.53mg/kg,均超出相关国家标准.方法的相对标准偏差为2.1％,加标回收率在94.8％-98.25％之间,检出限为0.0042μg/L.     

含氮SW缺陷对单壁碳纳米管电子结构和光学性质的影响

应用第一性原理密度泛函理论研究了单壁碳纳米管中Stone-Wales(SW)缺陷和氮掺杂情况下的电子结构和光学性质.研究发现,含氮SW缺陷单壁碳纳米管体系的总能降低,结合更稳定,且在费米能级附近出现一条半满的杂质带,并且随着氮掺杂位置的不同,掺杂能态出现显著差异.碳管的吸收和反射明显减弱且吸收峰和反射峰在低能区发生红移现象,在能量小于11eV附近均出现杂质特征峰.本文对计算结果进行了分析研究,可望为含氮SW缺陷碳管在光电材料中的应用提供理论依据. 关键词： 单壁碳纳米管 Stone-Wales缺陷 氮掺杂 光学性质     

Probing the structural and magnetic properties of transition metal-benzene anion complexes

Two types of transition metal-benzene anion complexes, (titanium)(n)(benzene)(m)? and (cobalt)(n)(benzene)(m)? (n ≤ 2, m ≤ 3) have been determined using density functional theory. The photoelectron spectra of Ti(n)Bz(m)? and Co(n)Bz(m)? (n ≤ 2, m ≤ 3) were discussed from the perspective of quantum chemical calculations of the vertical detachment energies (VDEs) of several low-energy isomers obtained by the structural optimization procedure. The binding of Ti and Co atoms to benzene molecules is accounted by 3d-π bonds, as revealed by the molecular orbitals. The topology of the electronic density has been analyzed, suggesting that the C-C bonds were weakened in the transition metal-benzene complexes in comparison to those in free benzene. Spin density distribution results show the spin densities for Ti(n)Bz(m)? and Co(n)Bz(m)? (n ≤ 2, m ≤ 3) reside mainly on the metal Ti and Co centers (70%-90%). A shift to lower magnetic moment with respect to the pure titanium/cobalt cluster anions indicates the solvent benzene molecule acts to demagnetize the bare titanium/cobalt cluster anions.