Theoretical Evaluation of Steric Effects in [ReH(5)(PR(3))(2)(SiR(3))(2)] Complexes with the IMOMM Method

A theoretical study including full geometry optimizations is carried out at the IMOMM(MP2:MM3) (IMOMM = integrated molecular orbital molecular mechanics) computational level on the [ReH(5)(PPh(i)()Pr(2))(2)(SiHPh(2))(2)] and [ReH(5)(PCyp(3))(2)(SiH(2)Ph)(2)] systems, the results being compared with available experimental diffraction data, as well as with MP2 results on the model system [ReH(5)(PH(3))(2)(SiH(3))(2)]. A simple scheme for the analysis of the relative weight of different contributions to the "steric" distortion is also proposed and applied to the same [ReH(5)(PPh(i)()Pr(2))(2)(SiHPh(2))(2)] and [ReH(5)(PCyp(3))(2)(SiH(2)Ph)(2)] species.     

Méthodes chimiques d'analyse des polyacroléines linéaires

Linear polyacroleins prepared by anionic polymerization give the structural repeat units of the types \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--}[{\rm CH}\left( {{\rm CHO}} \right)\hbox{--} {\rm CH}_{\rm 2} {\rm \rlap{--} ], \rlap{--} [CH}_{\rm 2} \hbox{--} {\rm CH}\left( {{\rm CHO}} \right)\rlap{--} ], $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm CH}\left( {{\rm CH}\hbox {\rm CH}_2 } \right)\hbox{\rm O\rlap{--} ]} $\end{document} without any cyclization. Analysis of these polymers by several methods reveal the nature and amount of each structural species, and an estimation of their distribution along the polymeric chain.     

On the structure of CH5+; A study of hydron transfer reactions from CH4H+ and CD4H+ tandem-ICR

Relative rates of proton and deuteron transfer from CH₄D⁺ and CD₄H⁺ to a number of molecules were examined in a tandem-ion cyclotron resonance instrument. The results were in conflict with the recent work of Sefcik et al. and support a randomized model.     

New green fluorescent polyvinylcarbazole copolymer with 1,8‐naphthalimide side chains as chemosensor for iron cations

The synthesis and basic photophysical characteristics of a novel green fluorescent polyvinylcarbazole polymer containing 4‐N,N‐dimethylaminoethyleneamino‐1,8‐naphthalimide side chains has been described. The ability to sense metal cations has been monitored by fluorescence emission spectroscopy. It is shown that the fluorescent intensity is very sensitive to the Fe²⁺ cations and the copolymer can be used as an homogeneous and heterogeneous fluorescent sensor for Fe²⁺ cations. Copyright © 2004 John Wiley & Sons, Ltd.     

Sodium 5‐nitro‐2‐pyridonate trihydrate

The title compound, alternatively sodium pyridin‐2‐olate trihydrate, Na⁺·C₅H₃N₂O₃^?·3H₂O, crystallizes in the P space group. It is made up of edge‐shared chains of NaO₆ octahedra with five water mol­ecules and one 5‐nitro‐2‐pyridonate anion. Four of these water mol­ecules are bicoordinating, involved in connecting the adjacent octahedra, and the fifth is coordinated to only one octahedron. The crystal structure is stabilized by a network of strong O—H?O and O—H?N interactions. The organic moieties occupy the space between the chains with an antiparallel alignment.     

Dirac's aether in relativistic quantum mechanics

The introduction by Dirac of a new aether model based on a stochastic covariant distribution of subquantum motions (corresponding to a vacuum state alive with fluctuations and randomness) is discussed with respect to the present experimental and theoretical discussion of nonlocality in EPR situations. It is shown (1) that one can deduce the de Broglie waves as real collective Markov processes on the top of Dirac's aether; (2) that the quantum potential associated with this aether's modification, by the presence of EPR photon pairs, yields a relativistic causal action at a distance which interprets the superluminal correlations recently established by Aspect et al.; (3) that the existence of the Einstein-de Broglie photon model (deduced from Dirac's aether) implies experimental predictions which conflict with the Copenhagen interpretation in certain specific testable interference experiments.     

Methane polymerization with a hollow cathode: Influence of the cathode metal

Methane, mixed with argon, has been polymerized by means of a hollow-cathode discharge system. Two types of cathodes were studied; one was made of a solid solution of 81% tungsten and 19% platinum, while the other was of pure tungsten. Under identical operating conditions, a higher polymer yield was found in the case of the platinum cathode (90% against 70% for tungsten). The work function of the solid solution was estimated to be 6.3 eV, compared with 4.4 eV for tungsten. In terms of the data available, the thermionic current, which is the main source of energetic electrons, is about one order of magnitude lower for the solid solution cathode when compared with the tungsten cathode thermionic current. However, the polymer yield observed is higher in the former case. The concentration of the CH species in the hollow cathode was found to differ greatly for the cathodes tested and was about 5 times higher in the case of tungsten-platinum cathodes. Since no excited platinum vapor could be detected in the gas phase, the increase in CH concentration was attributed to a catalytic effect of the cathode inside surface. An evaluation of the plasma polymer deposition rate yields 70 nm·s^–1 for the platinum-tungsten type hollow cathode and 42 nm·s^–1 for the tungsten one. In both cases, the deposition rate is much higher than those obtained from the most widely used methods for plasma polymer deposition (0.10–1.0 nm·s^–1) implying methane-argon mixtures, and is comparable to the results obtained with a new type of plasma polymer deposition reactor described in the literature.