A density functional theory computational study of the role of ligand on the stability of CuI and CuII species associated with ATRP and SET‐LRP

Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with Cu^I and trigonal bipyramidal with axial halide complexes with [Cu^IIX]⁺ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [Cu^IIX]⁺ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [Cu^IIX]⁺ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007     

Single photon and nonlocality

In a paper by Home and Agarwal [1], it is claimed that quantum nonlocality can be revealed in a simple interferometry experiment using only single particles. A critical analysis of the concept of hidden variable used by the authors of [1] shows that the reasoning is not correct.      

Pulsed gas lenses

The concept of a pulsed gas lens is proposed. Potential applications are envisaged and preliminary experiments with pulsed ray refraction are reported.     

布拉格方程在高聚物结构研究中的应用

本文将布拉格方程推广应用到高聚物的结构研究中，得到了经不同剂量辐照的聚乙烯单晶的长周期，并辅以示差扫描量热法研究了γ－射线辐照对聚乙烯单晶结构的影响．     

Density functional theory investigation of CN on Cu(1 1 1), Ni(1 1 1) and Ni(1 0 0)

The adsorption of CN on Cu(1 1 1), Ni(1 1 1) and Ni(1 0 0) has been investigated using density functional theory (DFT). While experimental studies of CN on Cu(1 1 1) show the molecular axis to be essentially parallel to the surface, the normally-preferred DFT approach using the generalised gradient approximation (GGA) yields a lowest energy configuration with the C-N axis perpendicular to the surface, although calculations using the local density approximation (LDA) do indicate that the experimental geometry is energetically favoured. The same conclusions are found for CN on Ni(1 1 1); on both surfaces bonding through the N atom is always unfavourable, in contrast to some earlier published results of ab initio calculations for Ni(1 1 1)/CN and Ni(1 0 0)/CN. The different predictions of the GGA and LDA approaches may lie in subtly different relative energies of the CN 5σ and 1π orbitals, a situation somewhat similar to that for CO adsorbed on Pt(1 1 1) which has proved challenging for DFT calculations. On Ni(1 0 0) GGA calculations favour a lying-down species in a hollow site in a geometry rather similar to that found experimentally and in GGA calculations for CN on Ni(1 1 0).     

Single electron transfer–degenerative chain transfer living radical polymerization of N‐butyl acrylate catalyzed by Na2S2O4 in water media

Living radical polymerization of n‐butyl acrylate was achieved by single electron transfer/degenerative‐chain transfer mediated living radical polymerization in water catalyzed by sodium dithionate. The plots of number–average molecular weight versus conversion and ln[M]₀/[M] versus time are linear, indicating a controlled polymerization. This methodology leads to the preparation of α,ω‐di(iodo) poly (butyl acrylate) (α,ω‐di(iodo)PBA) macroinitiators. The influence of polymerization degree ([monomer]/[initiator]), amount of catalyst, concentration of suspending agents and temperature were studied. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right‐angle light scattering (RALLS), a differential viscometer (DV), and refractive index (RI). The methodology studied in this work represents a possible route to prepare well‐tailored macromolecules made of butyl acrylate in an environmental friendly reaction medium. Moreover, such materials can be subsequently functionalized leading to the formation of different block copolymers of composition ABA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2809–2825, 2006     

Planned positron experiments at FRM-II

The new research reactor FRM-II near Munich has a strong positron source, which delivers an intense, nearly monoenergetic positron beam. Our positron systems, the pulsed low energy positron source (PLEPS) and the scanning positron microscope (SPM) will be operated at this beam. Some aspects of matching these systems to the new positron source will be discussed.Considerable improvements are expected, e.g. more than 10⁵ s⁻¹ recorded events at PLEPS and sub-micrometre resolution at SPM. They will enable investigations in so far inaccessible problems like the evaluation of annihilation characteristics and trapping constants of individual defects or studies of fast dynamical processes. In applied materials science complex defect structures will be studied which demand a resolution into many differing lifetimes, e.g. fractured specimens, wear, corrosion, etc. Also large series of measurements at small systematic modifications are planned. There is also the opportunity to analyse in addition the chemical microstructure of the specimens by means of a hydrogen microprobe and other ion beam techniques available close to FRM-II at the Technical University of Munich.     

A procedure for measuring the flexibility of single wood-pulp fibres

A way of determining the flexibility of wood-pulp fibres is developed, which involves i) a precise measurement of the topology of single-fibres by using a confocal laser scanning microscope and ii) the measurement of the elastic modulus of the fibres by using a single-fibre fatigue cell. Reported in this paper are the initial results of tests carried out on black spruce fibres, which have been subjected to three different levels of mechanical refining energy, namely ∼1100, 2300, and 3500 kWh/t. It is found that the fibre flexibility rises significantly between the first and second energy levels, but it does not change to the same degree between the second and third ones. The described procedure of measuring the flexibility of fibres may be used to establish the appropriate refiner energy necessary for the production of a specific grade of paper. Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 42, No. 1, pp. 115–128, January–February, 2006.     

应力对La0.83Sr0.17MnO3薄膜输运性能的影响

采用溶胶-凝胶方法在Si(111)上制备了LSMO(x=0.17)薄膜.研究了块体材料和不同厚度薄膜R -T曲线、红外光谱和X射线衍射.结果表明，LSMO薄膜属于正交晶体结构，薄膜取向与膜厚度 有关，当膜厚度为450nm或680nm时，主要取向〈200〉，而膜厚度为900nm时取向为〈020〉 ：根据离子对相互作用能和谐振子模型，得到了红外吸收与Mn—O—Mn键长和键角关系式，6 00cm^-1附近红外吸收与晶格常数b的变化有关；块体与薄膜的金属—绝缘体转变 温度(T_MI)存在较大差别，薄膜转变温度显著低于块体，并与厚度有一定关系. 认为是LSMO薄膜中的应力诱导了晶格常数变化，引起键角改变及JT效应是转变温度变化的主 要原因. 关键词： 单晶硅 晶格常数 金属—绝缘体转变温度 应力诱导     

An investigation of the 2D attractive Hubbard model

We present an investigation of the 2D attractive Hubbard model, considered as an effective model relevant to superconductivity in strongly interacting electron systems. We use both hybrid Monte-Carlo simulations and existing hopping parameter expansions to explore the low temperature domain. The increase of the static S-wave pair correlation with decreasing temperature, which depends weakly on the band filling in the explored temperature range, is analyzed in terms of an expected Kosterlitz-Thouless superconducting transition. Using both our data and previously published results, we show that the evidence for this transition is weak: If it exists, its temperature is very low. The number of unpaired electrons remains nearly constant with temperature at fixed attractive potential strength. In contrast, the static magnetic susceptibility decreases fast with temperature, and cannot be related only to pair formation. We introduce a method by which the Padé approximants of the existing series for the susceptibility give sensible results down to rather low temperature region, as shown by comparison with our numerical data. Received: 30 October 1996 / Revised: 23 October 1997 / Accepted: 29 January 1998