Barriers to internal rotation in biphenyl radical ions

Molecular orbital theory shows that the conformation of, and barriers to rotation in, radical ions of biphenyl derivatives are greatly different from those of the neutral compounds. The results are consistent with the ESR results on the cation radicals of some substituted biphenyls.     

Preparation and Properties of Single Crystals of Hydrogen Bis(Phthalocyaninato) Neodymium(III)

Single crystals of hydrogen bis(phthalo-cyaninato)neodymium(III) have been synthesized by electrochemical means. The crystals are semiconductors and follow Curie-Weiss behavior.     

Electronic Excitation of [(μ4‐η2‐alkyne)Rh4(CO)8(μ‐CO)2]: An In Situ UV/Vis Spectroscopy,Spectral Reconstruction and DFT Study

Reactions of three alkynes, namely, 1‐heptyne, 3‐hexyne and 1‐phenyl‐1‐butyne, with [Rh₄(CO)₉(μ‐CO)₃] are performed in anhydrous hexane under argon atmosphere with multiple perturbations of alkynes and [Rh₄(CO)₉(μ‐CO)₃]. The reactions are monitored by in situ UV/Vis spectroscopy, and the collected electronic spectra are further analyzed with the band‐target entropy minimization (BTEM) family of algorithms to reconstruct the pure component spectra. Three BTEM estimates of [(μ₄‐η²‐alkyne)Rh₄(CO)₈(μ‐CO)₂], in addition to that of [Rh₄(CO)₉(μ‐CO)₃], are successfully reconstructed from the experimental spectra. Time‐dependent density functional theory (TD‐DFT) predicted spectra at the PBE0/DGDZVP level are consistent with the corresponding BTEM estimates. The present study demonstrates that: 1) the BTEM family of algorithms is successful in analyzing multi‐component UV/Vis spectra and results in good spectral estimates of the trace organometallics present; and 2) the subsequent DFT/TD‐DFT methods provide an interpretation of the nature of the electronic excitation and can be used to predict the electronic spectra of similar transition organometallic complexes.     

New types of short-range orientational ordering in ortho-para hydrogen monolayers

Orientational ordering in monolayers of solid hydrogen is discussed in view of recent experimental findings in NMR studies of (ortho)_c-(para)_1−c-hydrogen mixtures on boron nitride substrate reported for ortho-H₂ concentrations 0.35≤c≤0.92 and temperatures 0.14≤T≤1.80 K. Analysis of the temperature-concentration behavior for the observed NMR frequency splitting is given on the basis of a two-dimension (J=1)_c-(J=0)_1−c-rotor model for which the fundamental parameters, quadrupolar coupling constant Γ₀=0.50±0.03 K and the crystal-field amplitude V₀=0.70±0.10 K, are derived from experiment. The two distinct para-rotational (PR) short-range ordered structures driven by positive and negative crystalline fields are described in terms of the local alignment and orientation of the polar principal axis. It is shown that they are rather different from the ferromagnetic-type ordering suggested earlier by Harris and Berlinsky as a unique PR structure. The common quadrupolar glass and a new hindered rotor phases found below the 2D site percolation threshold c_p=0.72 are also discussed.     

过渡金属类立方烷原子簇化合物电子结构和二阶非线性光学性质的密度泛函理论研究

采用基于第一原理的含时密度泛函理论(TDDFT)对一系列具有类立方烷簇芯结构的过渡金属簇合物二阶非线性光学性质进行了研究。结果证明, 由于簇芯结构的对称性的影响, 这一类簇分子的二阶非线性光学系数的数值要小于三核欠完整类立方烷体系。通过对电子结构的分析, 发现二阶非线性光学性质主要是由簇芯内电荷的迁移造成的。轨道分析显示, -S原子对于电荷的迁移起主要的传递作用。定域化轨道分析证明簇分子中存在的多中心键有利于簇芯内电荷的迁移。分子模拟的研究表明:虽然类立方烷结构簇分子的值比较小, 但是通过合理的配体设计, 获得具有较大值非线性光学晶体是可能的。     

Coupling of mixed finite elements and boundary elements

The symmetric coupling of mixed finite element and boundaryelement methods is analysed for a model interface problem withthe Laplacian. The coupling involves a further continuous ansatzfunction on the interface to link the discontinuous displacementfield to the necessarily continuous boundary ansatz function.Quasi-optimal a priori error estimates and sharp a posteriorierror estimates are established which justify adaptive mesh-refiningalgorithms. Numerical experiments prove the adaptive couplingas an efficient tool for the numerical treatment of transmissionproblems.     

ChemInform Abstract: Thermochemistry of N3O2‐

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