Electron-phonon interaction in tetrahedral semiconductors

Considerable progress has been made in recent years in the field of ab initio calculations of electronic band structures of semiconductors and insulators. The one-electron states (and the concomitant two-particle excitations) have been obtained without adjustable parameters, with a high degree of reliability. Also, more recently, the electron-hole excitation frequencies responsible for optical spectra have been calculated. These calculations, however, are performed with the constituent atoms fixed in their crystallographic positions and thus neglect the effects of the lattice vibrations (i.e. electron-phonon interaction) which can be rather large, even larger than the error bars assumed for ab initio calculations.Effects of electron-phonon interactions on the band structure can be experimentally investigated in detail by measuring the temperature dependence of energy gaps or critical points (van Hove singularities) of the optical excitation spectra. These studies have been complemented in recent years by observing the dependence of such spectra on isotopic mass whenever different stable isotopes of a given atom are available at affordable prices. In crystals composed of different atoms, the effect of the vibration of each separate atom can thus be investigated by isotopic substitution. Because of the zero-point vibrations, such effects are present even at zero temperature (T=0).In this paper, we discuss state-of-the-art calculations of the dielectric function spectra and compare them with experimental results, with emphasis on the differences introduced by the electron-phonon interaction. The temperature dependence of various optical parameters will be described by means of one or two (in a few cases three) Einstein oscillators, except at the lowest temperatures where the T⁴ law (contrary to the Varshni T² result) will be shown to apply. Increasing an isotopic mass increases the energy gaps, except in the case of monovalent Cu (e.g. CuCl) and possibly Ag (e.g. AgGaS₂). It will be shown that the gaps of tetrahedral materials containing an element of the first row of the periodic table (C,N,O) are strongly affected by the electron-phonon interaction. It will be conjectured that this effect is related to the superconductivity recently observed in heavily boron-doped carbon.     

Alkylation of 2,3,6,11-tetrahydroanthra[2,1-d]isothiazole-3,6,11-trione and its S-oxide

The reactions of 2,3,6,11-tetrahydroanthra[2,1-d]isothiazole-3,6,11-trione with dimethyl sulfate, benzyl chloride, and allyl bromide afforded the corresponding 2-alkyl-2,3,6,11-tetrahydroanthra[2,1-d]isothiazole-3,6,11-triones and 3-(alkoxy)-6,11-dihydroanthra[2,1-d]isothiazole-6,11-diones. The reactions of 2,3,6,11-tetrahydroanthra[2,1-d]isothiazole-3,6,11-trione and its S-oxide with a formaldehyde—secondary amine system yielded 2-[(alkylamino)methyl]-2,3,6,11-tetrahydroanthra[2,1-d]isothiazole-3,6,11-triones and 2-[(alkylamino)methyl]-3,6,11-trioxo-2,3,6,11-tetrahydroanthra[2,1-d]isothiazole 1-oxides, respectively.     

温度对PSⅡCP4 7/D1/D2/Cytb559复合物荧光光谱特性的影响

采用激励光源为514.5 nm的分幅扫描单光子计数荧光光谱装置对经20℃、42℃和48℃不同温度处理后的反应中心复合物CP47/D₁/D₂/Cyt b559的荧光光谱特性进行了研究.经解析,获得不同温度处理后,CP47/D₁/D₂/Cyt b559复合物最大峰值未发生变化,均在682 nm,说明Chla670的能量都由Chla682接收,但损耗愈来愈小,在48℃时,损耗程度最小,而其荧光百分比未发生多大变化.振动副带～700 nm和～740 nm的中心波长都发生蓝移,在不同温度下分别为:20℃ 703 nm,749 nm;42℃ 697 nm,744 nm;48℃ 694 nm,740 nm.因此可以推测温度的升高,影响了CP47/D₁/D₂/Cyt b559色素蛋白的二级结构以及色素分子的空间位置,使最大峰值处的荧光强度逐渐降低,振动副带逐渐蓝移.42℃的温度已造成影响,48℃影响较大.     

用毛细管测量纯水表面张力系数的误差讨论

通过用毛细管测量纯水表面张力系数实验，得到管内径d与接触角θ的相对误差之间的关系曲线，由此说明实验测得的表面张力系数α和理论公式相比呈现一定的偏差，并简单地讨论了实验的理想状态与实际情况的差别．     

Excess molar enthalpies of binary mixtures of 1-hexene with some cyclic and aromatic hydrocarbons at 298.15 K

Microcalorimetric measurements of excess molar enthalpies, at 298.15 K, are reported for the four binary systems formed by mixing 1-hexene with the cycloalkanes: cyclohexane and methylcyclohexane, and with the aromatic hydrocarcons: benzene and toluene. Smooth Redlich-Kister representations of the results are presented. It was found that the Liebermann-Fried model also provided good representations of the results.     

1H and 13C NMR spectroscopic study of oxidation of D,L‐cystine and 3,3′‐dithiobis(propionic acid) with hydrogen peroxide in aqueous solution

The oxidation of symmetrical disulfides [D ,L ‐cystine ( 1 ) and 3,3′‐dithiobis(propionic acid) ( 2 )] with hydrogen peroxide in D₂O–NaOH solution (pH 10–11) was studied by NMR spectroscopy. Assignments of the proton and carbon NMR signals of starting materials ( 1 and 2 ) and products of oxidation are based on conventional 1D NMR methods (DEPT, selective spin decoupling). Formation of C—S bond cleavage products or, in case of 2 , partially oxidized intermediates was not detected. The accelerating effect of Cu²⁺ cations, but not Fe³⁺ cations, on the oxidation rate of 1 in basic medium was demonstrated. Copyright © 2002 John Wiley & Sons, Ltd.     

Equisingular Deformations of Sandwiched Singularities

We relate the equisingular deformation theory of plane curve singularities and sandwiched surface singularities. We show the existence of a smooth map between the two corresponding deformation functors and study the kernel of this map. In particular we show that the map is an isomorphism when a certain invariant is large enough.     

A test problem for molecular dynamics integrators

We derive a test problem for evaluating the ability of time-steppingmethods to preserve the statistical properties of systems inmolecular dynamics. We consider a family of deterministic systemsconsisting of a finite number of particles interacting on acompact interval. The particles are given random initial conditionsand interact through instantaneous energy- and momentum-conservingcollisions. As the number of particles, the particle density,and the mean particle speed go to infinity, the trajectory ofa tracer particle is shown to converge to a stationary Gaussianstochastic process. We approximate this system by one describedby a system of ordinary differential equations and provide numericalevidence that it converges to the same stochastic process. Wesimulate the latter system with a variety of numerical integrators,including the symplectic Euler method, a fourth-order Runge-Kuttamethod, and an energyconserving step-and-project method. Weassess the methods' ability to recapture the system's limitingstatistics and observe that symplectic Euler performs significantlybetter than the others for comparable computational expense.     

三苯甲基自由基及其二聚体稳定性的理论研究

采用量子化学AM1 MO方法优化了三苯甲基自由基及其两种二聚体的构型，并计算了反应物和二聚物的生成焓、活化能以及它们的电荷布居，计算结果表明，三苯甲基自由基是一种较稳定的自由基，在这个自由基中存在明显的共轭效应，分子中电子云呈平均化分布．它的二聚体1，4—环己二烯衍生物分子中的5个苯基排布在环己二烯环平面的两端，明显降低了苯基之间的空间排斥力，使二聚物—环己二烯衍生物分子的稳定性大大高于六苯乙烷．因此，三苯甲基自由基的二聚体是1，4—环己二烯衍生物而不是六苯基乙烷，得到了与实验事实一致的结果。