Central moments in quantum chemistry

We define central moments of operators on finite‐dimensional vector spaces and study some of their basic aspects. Central moments may be viewed as generalizations of the dispersion of a Hermitian operator. We show how eigenvalues may be represented by central moments, and how central moments may be used to obtain Krylov subspace approximations for operators on inner product spaces. We show that central‐moments approximations are compatible with the concepts of size‐consistency in quantum chemistry, and we use this to suggest a foundation for central‐moments approximations in Coupled Cluster theory. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Chemical activity of the nitrogenase FeMo cofactor with a central nitrogen ligand: density functional study

We investigate the chemical consequences of a central ligand in the nitrogenase FeMo cofactor using density functional calculations. Several studies have shown that the central ligand most probably is a nitrogen atom, but the consequences for the chemical reactivity of the cofactor are unknown. We investigate several possible routes for insertion of the central nitrogen ligand and conclude that all routes involve barriers and intermediate states, which are inaccessible at ambient conditions. On this basis we suggest that the central nitrogen ligand is present at all times during the reaction. Furthermore, we investigate how the FeMoco with the central ligand can interact with N(2) and reduce it.     

线性非理想条件下液相色谱柱末端峰形规律

 色谱流出曲线的二阶中心矩μ２和三阶中心矩μ３以及描述峰形非对称程度的偏态系数∑ｋ＝μ３／μ１．５２是反映色谱峰形的重要参数。从液相色谱过程动力学方程出发，运用电子计算机证明了在线性非理想条件下高效液相色谱体系中不同保留值组分在柱末端峰形的分布基本一致的结论。     

Anisotropic wetting on checkerboard-patterned surfaces

A series of surfaces with microscale checkerboard patterns consisting of continuous central lines and discontinuous lateral lines were fabricated. The surface wetting properties of these checkerboard patterns were found to be anisotropic. The central continuous lines were found to have a strong influence on the dynamic wetting properties and moving trajectories of the water droplets. The droplets move more easily in the direction parallel to the central continuous lines and less easily in the direction perpendicular to the central continuous lines. Meanwhile, the droplets' moving path tends to incline toward the central continuous lines from a tilting direction. When the microsurface was modified with a layer of nanowire, the surface wettability was found to be isotropic and superhydrophobic.     

NMR titration and molecular model MOPAC calculation of protonation processes of two MRI ligands

The protonation process of two DTPA bis(amide) derivatives,DTPA-BDMA and DTPA-BDEA,was studied by using 1H NMR titration and MOPAC calculation.Their protonation process was proposed in the order of the central amine,the terminal amines,the central carboxyl,the terminal carboxyl,the other terminal carboxyl and central amine.During the protonation of the terminal amine,there existed a large fraction of proton transfer from the central amine to the other terminal amine.     

线性非理想条件下液相色谱柱末端峰形规律

色谱流出曲线的二阶中心矩μ２和三阶中心矩μ３以及描述峰形非对称程度的偏态系数∑ｋ＝μ３／μ１．５２是反映色谱峰形的重要参数。从液相色谱过程动力学方程出发，运用电子计算机证明了在线性非理想条件下高效液相色谱体系中不同保留值组分在柱末端峰形的分布基本一致的结论。     

Ar的第三谱带240nm中心谱区与气压关系的实验观察

采用强流相对论电子束横向泵浦纯氩,获得了属于Ar的第三谱带范围内240nm中心谱区的光强随气压变化的关系.结果表明,压强为3×10⁵Pa时是产生这一谱区的最佳气压,并证实了这一谱区是由带电的原子团簇产生的.     

Mapping the light field of the Waldmann PDT 1200 lamp: potential for wide-field low light irradiance aminolevulinic acid photodynamic therapy

A quantitative assessment of the light field produced by a Waldmann PDT 1200 lamp is presented. A photodiode detector array capable of measuring a beam diameter of 30 cm was used to map the light field. The irradiance was measured as a function of voltage. For lamp-detector distances of 10 cm (central axis irradiance = 250 mW/cm2), the spatial profile of irradiance was typically Gaussian. For lamp-detector distances of 30 cm (central axis irradiance = 79 mW/cm2), the spatial profile appeared more hemispherical in shape but with some asymmetry. The relative percentage variation between the maximum and minimum irradiance with respect to the central axis irradiance was approximately 13% and 3%, respectively, for a beam width of 12 cm. Beyond a lamp-detector distance of 50 cm (central axis irradiance = 32 mW/cm2), the spatial profile of irradiance was observed to become more crater-like in structure, with a minimum on the central axis and an approximately symmetric peak at a radial distance of 9 cm from the center. The relative percentage variation of this peak irradiance with respect to the central axis irradiance was approximately 17%. At lamp-detector distances of 70 and 90 cm (central axis irradiance = 19 and 13 mW/cm2, respectively), the beam's profile was asymmetric, and the irradiance was observed to increase from the center to a radial distance of 15 cm (beam width 30 cm). For a lamp-detector distance of 70 and 90 cm, the relative percentage variation between the maximum irradiance and the central axis irradiance was approximately 25% and 35%, respectively.     

Dielectric behaviour of liquid crystals with a pyramidal central unit

Dielectric measurements of oligomeric cyanobiphenyls connected to a pyramid-like central unit are presented. The data are interpreted in terms of the dynamics of the liquid crystalline units. There is no indication of reorientation of the central unit as whole or co-operative effects of piled up central units.     

双[对-N,N-二甲基氨基苄叉]酮类化合物光谱和光物理行为的研究

本工作研究了几种中心部分被束缚的双[对-N,N-二甲基氨基苄叉]酮类化合物的光物理行为.发现中心五元环的化合物比中心六元环的化合物有着高得多的荧光量子产率,在改变介质粘度、研究粘度对荧光量子产率的影响时发现中心六元环化合物最易受粘度变化的影响,对上述这些有趣的现象进行了扼要的分析和讨论.     

Modeling a central ligand in the nitrogenase FeMo cofactor

In very recent work by Einsle et al. (Science 2002, 297, 1696), a new X-ray crystallographic structure of the FeMo cofactor of nitrogenase with a central ligand was presented. The central ligand is a light atom (N, O, or C), and Einsle et al. suggest that it is nitrogen. We present density functional calculations on the FeMo cofactor, and we investigate N, O, and C as central ligands. We show that both N and O lead to energetically stable FeMo cofactor structures, whereas C is energetically unfavorable. By comparison of bond geometries with the crystallographically determined values, we show that the central ligand is most likely nitrogen.     

二缺位γ-Keggin型多金属氧酸盐电子性质的密度泛函理论研究

采用密度泛函理论(DFT)方法研究了二缺位γ-Keggin型[γ-Xn+W10O36](12-n)-(X=AlⅢ,SiⅣ,PⅤ,SⅥ,GaⅢ,GeⅣ,AsⅤ,SeⅥ)阴离子的儿何结构和电子性质结果表明,在二缺位γ-Keggin型阴离子中,中心四面体氧原子Oa与中心杂原子及钨原子间的键长[d(X-Oa)及d(W-Oa)]...     

Theoretical Study of the Geometry of Dibenzoazepine Analogues

The geometry of dibenzoazepine analogues—typical multifunctional drugs—was investigated to find the geometrical parameters sensitive to the substitution of the central seven-membered ring. Exploration of the crystal structure database (CSD) shows that the geometrical parameter sensitive to the substitution of the carbon atom distance of the central ring not included in the aromatic rings to the plane through the carbon atoms common for the central ring and the aromatic side rings. Presence of the double bond in the central ring was reflected in its partial aromaticity expressed by the HOMED parameter. Some derivatives of 5H-dibenzo[b,f]azepine with flat conformation of the central ring are characterized by mobility of the electron density comparable to the mobility in the aromatic side rings. Influence of the surrounding on the investigated compounds was confirmed by comparison of the optimized molecules and the molecules in the crystal state where the packing forces can influence the molecular geometry.     

New symmetric azobenzene molecules of varied central cores: Synthesis and characterisation for liquid crystalline properties

A new series of azobenezene liquid crystals (LCs) was designed and synthesised by known and straightforward methods. The central connecting cores of the molecules varied viz., benzene/naphthalene/biphenyl. The molecular structures were confirmed by infrared, UV, nuclear magnetic resonance spectroscopic techniques. The LC texture and thermal phase behaviours were investigated by polarising optical microscopy and differential scanning calorimetry. Smectic B phase was found in biphenyl-derived azobenzene ester. The effect of central core on LC properties was investigated. The decreased angle at central connecting core suppressed the melting points, phase transition temperatures without losing LC properties, whereas, in moderate angle compounds LC properties were suppressed. The compounds with increased angle at central core favours rich mesomorphism.     

On the Mechanism of Polyurethane Formation Catalyzed by Metal Chelates and Organotin Compounds

The mechanism of the catalyzed linear polyurethane formation in the presence of dibutyltin dilaurate, copper acetylacetonate, and similar catalysts was investigated. It was found that the central ion coordinates with the isocyanate group. The second reacting component may be coordinated by the organic substituent or ligand groups near the central ion. It was concluded that the catalytic mechanism would vary depending on such reaction conditions as temperature, solvent, and the nature of the ligands near the central ion.     

On the theory of structural transformations in polar colloids

Structural transformations in the ensemble of particles with permanent intrinsic dipole moment are theoretically studied. In addition to dipole-dipole component, interparticle potential includes central attractive interaction. Such systems belong to ferrocolloids (ferrofluids) whose particle central molecular interaction is not completely screened by the protective surface layers, to polar molecular liquids, and other similar media. Main attention is focused on the analysis of chain-dense globule transitions in particle ensembles. The obtained results demonstrate that even weak central interaction between particles can induce such a transition. The performed studies explain why, in most of the known computer experiments with polar particles, the formation of dense bulk phases is observed only at the presence of central interparticle attraction and only dipole-dipole interaction results in the formation of linear chain structures, but not bulk phases.     

Enantioseparation of α‐hydroxy acids by chiral ligand exchange CE with a dual central metal ion system

Using two kinds of central metal ions in a background electrolyte, ligand exchange CE was investigated for the simultaneous enantioseparation of dl ‐malic, dl ‐tartaric, and dl ‐isocitric acids. Ligand exchange CE with 100 mM d ‐quinic acid as a chiral selector ligand and 10 mM Cu(II) ion as a central metal ion could enantioseparate dl ‐tartaric acid but not dl ‐malic acid or dl ‐isocitric acid. A dual central metal ion system containing 0.5 mM Al(III) ion in addition to 10 mM Cu(II) ion in the background electrolyte enabled the simultaneous enantioseparation of the three α‐hydroxy acids. These results suggest that the use of a dual central metal ion system can be useful for enantioseparation by ligand exchange CE.     

单臂冠醚结构与液晶性质

设计并合成了4个单臂冠醚液晶,考察了冠醚环与亲酯性结构单元之间的桥键与液晶性质的关系,中心桥键对单臂冠醚液晶的熔点影响不大,而对液晶热稳定性有较大的影响.     

配位聚合物的三阶非线性光学性质

本文概括了配位聚合物的三阶非线性光学性质，并总结了其结构与三阶非线性光学性质之间的关系。对于一维结构的配位聚合物，因配体不同或者中心金属离子的价层电子构型不同可呈现自聚焦或自散焦效应;二维结构配位聚合物的三阶非线性光学性质则与配体和中心金属离子无关，均呈现自聚焦效应;三维结构配位聚合物的自聚焦或自散焦效应主要受中心金属离子价层电子构型的影响。     

Substituent effects on the redox properties and structure of substituted triphenylamines. An experimental and computational study

The peak oxidation potentials of a series of polysubstituted triphenylamines were found to be highly linearly correlated (R=0.995) with their ionization potentials as computed by density functional theory. The computations, as well as confirming previous experiments demonstrating the planar geometry of such substances around the central nitrogen atom, also demonstrate substantial resonance interactions between the central nitrogen atom and a nitro group located para or ortho to it; no such interaction is involved in the corresponding amine cation radicals. On the other hand, a methoxy group located para to the central nitrogen atom interacts strongly with the central nitrogen in the cation radical, but not in the neutral amine.