不饱和类硅烯H2C=SiNaF的DFT研究

用密度泛函理论方法, 在B3LYP/6-31+G(d, p)水平上研究了不饱和类硅烯H2C=SiNaF的结构. 结果表明, 不饱和类硅烯H2C=SiNaF共有四种平衡构型, 其中非平面的p-配合物型构型能量最低, 是不饱和类硅烯H2C=SiNaF存在的主要构型. 对平衡构型间异构化反应的过渡态进行了计算, 求得了转化势垒. 计算预言了最稳定构型的振动频率和红外强度.     

Electrodeposition mechanism of Ni?Mo?P alloy in the solution of ammoniac citrate

The induced codeposition mechanism of Mo, P and Ni from the solution of ammoniac citrate was studied by means of steady-state polarization, AC impedance and X-ray Photoelectron Spectroscopy (XPS). The result of electrochemical measurements proved that [NiCit(NHs)₂]- is the electro-active species of nickel, though nickel ions exist mainly as [NiCit(NH₃)₃]^? in ammoniac citrate. XPS experiments proved the existence of tetravalent molybdenum corresponding to MoO₂ on the surface of mme deposits. The intermediate product, MoO₂, WM probably reduced to Mo in the alloy deposit by atomic hydrogen adsorbed on the induced metal nickel. The reduction of H₂PO^?₂ occurs through two distinctive steps with PH₃ an an intermediate, which subsequently reacts with atomic hydrogen to form P in the alloy deposit. The electrodeposition mechanism was proposed in this paper.     

Crystal Radii and Their Application on the Study of Electronic Structures of LaX(X=N,P,As,Sb)

以Ｐｈｉｌｉｐｓ－ＶａｎＶｅｃｈｔｅｎ理论和晶体光学性质为基础，计算了ＬａＸ（Ｘ＝Ｎ，Ｐ，Ａｓ，Ｓｂ）晶体的离子半径（单位：ｎｍ）：（Ｌａ：Ｎ）为（０．１４１４，０．１２３６），（Ｌａ：Ｐ）为（０．１５１８，０．１４８９），（Ｌａ：Ａｓ）为（０．１５３６，０．１５２６），（Ｌａ：Ｓｂ）为（０．１５８６，０．１６５１）．用ＬＭＴＯ－ＡＳＡ方法对ＬａＸ系列晶体的能带结构进行了计算．所得到的能隙是：ＬａＮ为２．３０ｅＶ，ＬａＰ为２．０５ｅＶ，ＬａＡｓ为１．６６ｅＶ，ＬａＳｂ为１．３４ｅＶ．与实验结果相符．这也证明了作者得到的半径的合理性．     

Fine-tuning the electronic properties of highly stable organometallic Cu(III) complexes containing monoanionic macrocyclic ligands

A family of highly stable organometallic Cu(III) complexes with monoanionic triazamacrocyclic ligands (L(i)) with general formula [CuL(i)]+ have been prepared and isolated, and their structural, spectroscopic, and redox properties thoroughly investigated. The HL(i) ligands have been designed in order to understand and quantify the electronic effects exerted by electron donor and electron-withdrawing groups on either the aromatic ring or the central secondary amine or on both. In the solid state the Cu(III) complexes were mainly characterized by single-crystal X-ray diffraction analysis, whereas in solution their structural characterization was mainly based on 1H NMR spectroscopy given the diamagnetic nature of the d(8) square-planar Cu(III) complexes. Cyclic voltammetry together with 1H NMR and UV/Vis spectroscopy have allowed us to quantify the electronic effects exerted by the ligands on the Cu(III) metal center. A theoretical analysis of this family of Cu(III) complexes has also been undertaken by DFT calculations to gain a deeper insight into the electronic structure of these complexes, which has in turn allowed a greater understanding of the nature of the UV/Vis transitions as well as the molecular orbitals involved.     

Lattices and infinite-dimensional forms. ‘The Lattice Method’

Hermitean vector spaces E of infinite dimensions are considered. Let G be a subgroup of the orthogonal group of E acting on a set M. The Lattice Method is a technique for classifying the orbits in M under G. We discuss the method in abstract terms and we illustrate it by means of three classification results showing that it is decisive to do a considerable amount of explicit calculations with vector subspace lattices.     

Infrared lattice bands of some pearls

From analysis of anisotropical lattice bands properties of 50 reflection spectra both of the CO stretching and bending bands measured from some pearl (Ca⁺⁺CO ₃ ^–– or Ca⁺⁺HCO ₃ ^–– layer) we discussed following subjects.i) Quantized properties present both in reflectivity and in energy. ii) classifications of the Optical Activity. iii) Polar distributions of the CO₃ oscillators in Ca⁺⁺CO ₃ ^–– surface mono-layer. iv) Force constants of these oscillators. v) Step variation of the dipolemoment and their influences to the degree of Optical Activity. vi) Two types of hysteresis loops of the values of Y_N (M_2Jbend ()/M_1Jstret. ()) derived from the oscillators which are at innert-state, at weak active-state and at active-state.