Structures and stability of N7+ and N7− clusters

Ab initio molecular orbital theory and density functional theory have been used to study nine isomers of N₇ ionic clusters with low spin at the HF/6-31G*, MP2/6-31G*, B3LYP/6-31G*, and B3LYP/6-311(+)G* levels of theory. All stationary points are examined with harmonic vibrational frequency analyses. Four N₇ ⁺ isomers and five N₇ ⁻ isomers are determined to be local minima or very close to the minima on their potential-energy hypersurfaces, respectively. For N₇ ⁺ and N₇ ⁻, the energetically low lying isomers are open-chain structures (C _{2 v} and C _{2 v} or C₂). The results are very similar to those of other known odd-number nitrogen ions, such as N₅ ⁺, N₉ ⁺, and N₉ ⁻, for which the open-chain structures are also the global minima. This research suggests that the N₇ ionic clusters are likely to be stable and to be potential high-energy-density materials if they could be synthesized. Received: 16 July 2001 / Accepted: 8 October 2001 / Published online: 21 January 2002     

From a point-like to an arbitrarily shaped sample: A survey of equations for electron paramagnetic resonance signal intensity calculations

A set of original, analytical equations useful for theoretical calculation of the electron paramagnetic resonance (EPR) signal intensity are presented for the multitude of sample shapes, which range from point-like, line-like, planar, rectangular, cubical, circular, cylindrical, spherical to an irregularly shaped sample. The samples can be situated at any available position within the prescribed part of the microwave cavity (a central cylinder of diameter 11 mm and length 23.5 mm, in either a Bruker single TE₁₀₂ or double TE₁₀₄ rectangular cavity, with the modulation coils situated in the left and right side cavity walls, which is connected to a X-band, field-modulated CW Bruker EPR spectrometer). The theoretical computations of EPR signal intensity can be used in the computer simulations in which: (i) the EPR signal intensity profiles are constructed; (ii) the optimal sample positions in the cavity to give a maximum value of signal intensity are found; (iii) the errors associated with sample positioning within the cavity when compared to a second sample of a different size, shape or position are studied.     

Kinetic-catalytic determination of traces of iron by the oxidative coupling reaction of 3-methyl-2-benzothiazolinone hydrazone with N,N-dimethylaniline

A new kinetic-catalytic method by the initial rate procedure for the determination of nanogram level of iron(III) is developed, which is based on its catalytic effect on the oxidative coupling of 3-methyl-2-benzothiazolinone hydrazone (MBTH) with N,N-dimethylaniline (DMA) to form an indamine dye (λ_max=590 nm) in the presence of hydrogen peroxide. Iron(II) is also determined, being oxidized to iron(III) by hydrogen peroxide. Calibration graphs obtained by the initial rate method are linear in the range 1–1000 ng ml⁻¹ Fe and as low as 10⁻⁸ M Fe(II, III) can easily be determined. The relative standard deviations are 6.6, 2.5 and 1.5% for ten determinations of 1, 20 and 60 ng ml⁻¹ of Fe(III), respectively. The method is applicable to the determination of iron in natural waters without preconcentration and separation.     

纳米硅胶颗粒的制备及其对金属离子的识别

利用sol-gel方法制得了纳米级的硅胶悬浮液.通过表面化学修饰引入了具有发射荧光能力的萘基基团.在稳态荧光研究中清晰地观察到在微小粒子表面上萘基基团会因溶剂不同而发生重新排组,并呈现出激基缔合物发光.研究了不同过渡金属离子对粒子表面荧光的猝灭效应,发现只有Cu2＋对纳米微球荧光有强烈的猝灭特征,这种优良的选择能力使其有望发展成为一种分析检测Cu2＋的荧光化学敏感器.     

An extended PCILO method

The perturbative configuration interaction using localized orbitals (the PCILO method) was extended in the way that current limitations to the two-centre bond approach were overcome. The localized molecular orbitals contain an arbitrary number of the basis set components; this follows from the a priori stated localized bonding model of a molecule. The extended PCILO method was formulated for the CNDO, INDO and NDDO Hamiltonian approximations. The configuration interaction was performed using the Rayleigh-Schrödinger many-body perturbation theory with the Møller-Plesset type of Hamiltonian partitioning, similar to that used in the so-called modified PCILO method. Applications to molecules with semi-localized and/or semi-delocalized bonds, as benzene or diborane, are presented.     

Conjugate-gradient method for computing the Moore-Penrose inverse and rank of a matrix

A conjugate-gradient method is developed for computing the Moore-Penrose generalized inverseA of a matrix and the associated projectors, by using the least-square characteristics of both the method and the inverseA . Two dual algorithms are introduced for computing the least-square and the minimum-norm generalized inverses, as well asA . It is shown that (i) these algorithms converge for any starting approximation; (ii) if they are started from the zero matrix, they converge toA ; and (iii) the trace of a sequence of approximations multiplied byA is a monotone increasing function converging to the rank ofA. A practical way of compensating the self-correcting feature in the computation ofA is devised by using the duality of the algorithms. Comparison with Ben-Israel's method is made through numerical examples. The conjugate-gradient method has an advantage over Ben-Israel's method.After having completed the present paper, the author received from Professor M. R. Hestenes his paper entitledPseudo Inverses and Conjugate Gradients. This paper treated the same subject and appeared in Communications of the ACM, Vol. 18, pp. 40–43, 1975.     

An intermediate spherical model of a ferromagnet

A one-parameter family of partition functions is considered which for zero value of the parameter reduces to the spherical model of a ferromagnet. The model for > 0 is closer to the usual discrete lattice spin model of a ferromagnet than is the spherical model. The first four terms in of the limiting value of the partition function are calculated above and below the critical temperature for arbitrary interactions using the saddle point method to calculate certain correlation functions for the spherical model. These calculations indicate that the critical temperature is independent of for small and certain interactions.Part of this research appeared in the author's doctoral thesis.⁽³⁾     

Position-space renormalization for systems with weak long-range interactions and the breakdown of hyperscaling

Exact renormalization group equations are derived for a position-space renormalization of spin systems with weak long-range forces. It is shown how an apparent dependence of the critical exponents on the choice of the renormalization group can be resolved via the mechanism of dangerous irrelevant variables and that this same mechanism is responsible for the breakdown of hyperscaling. The dimensiond=4 can be seen to be a borderline dimension above which classical critical exponents are expected.     

链珠状氢氧化亚镍的准电容特性及其在复合型超电容器中的应用(英)

本文采用溶胶凝聚方法制备了超细氢氧化亚镍电极材料并通过在其中掺加适量碳纳米管的方法大大提高了电极的比容量并有效改善了电极材料的阻抗特性。掺有20%碳纳米管的氢氧化亚镍复合电极材料的单电极比容量可达到320 F·g^-1。本文分别采用氢氧化亚镍/碳纳米管复合电极作为正极，活性炭作为负极，6 mol·L^-1 KOH作为电解液制备了复合型电化学电容器。采用上述方法制备的复合型电容器工作电压达到1.6 V，电容器质量比容量达到60 F·g^-1。复合型电容器能量密度达到20.11 Wh·kg^-1，最大功率密度达到8.6 kW·kg^-1,兼具高能量特性和优良的大电流放电特性。     

多孔二氧化硅中Gd3+ → Eu3+的能量传递

通过水热反应法，获得了单掺和双掺Eu³⁺，Gd³⁺的多孔二氧化硅组装体，研究了掺杂体系的光谱特性，观察到Gd³⁺ → Eu³⁺的能量传递。分析了能量传递过程，探讨了在多孔二氧化硅中Gd³⁺→Eu³⁺的能量传递的机理，其机理主要为电偶极-电偶极相互作用。