Electronic structure of the benzene–tetracyanoethylene complex: A synthesis of molecular orbital and density functional descriptions

The electronic structure of the benzene–tetracyanoethylene electron donor–acceptor complex is investigated at the HF /6-311G ^** level of theory. The computed electronic wave function is analyzed with rigorous interpretive tools that involve both molecular orbital and density functional approaches. The in situ electronegativity difference is calculated at 3.32 eV, resulting in a charge transfer of 0.016. This extent of charge transfer is found to account for only ca. 17% of the interaction energy of ca. 33% of the dipole moment. The remaining part of the dipole moment originates from buckling of the tetracyanoethylene moiety. The dependence of the electronegativity difference on the magnitude of charge transfer is found to be highly nonlinear. © 1994 John Wiley & Sons, Inc.     

The plasticity of the Cu(H2O) 6 2+ Jahn-Teller complex affected by lattice strains and cooperative interactions

The EPR spectra evolution of Cs₂Zn_1?x Cu_x(ZrF₆)₂ · 6H₂O (x=0.01, 0.6, 0.8, and 1.0) in the temperature range 4.2–330 K and the x-ray structure analysis of the compound with x=1.0 in the range 150–327 K show that the Jahn-Teller (JT) complex Cu(H₂O)₆ coordination sphere undergoes a plastic deformation. The observed effect is due to the combined influence of small lattice strains existing in the paraphase and a new one appearing as a result of a ferroelastic phase transition and increasing with decreasing temperature below T _c . It is proved that both cooperative interactions between JT complexes and ferroelastic strain stabilize a certain JT configuration. The problem of instability of a JT configuration compressed at T ～ 265 K is discussed.     

Structure and electrochemical behaviour of 4,7-diazaheptyl-trimethoxy-silane and vinyl-trialkoxy-silane adsorbed at silver surface

Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li⁺ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods.     

LocalH-theorem for a kinetic variational theory

A localH-theorem is derived for a recently proposed extension of Enskog kinetic theory to a dense model fluid composed of particles with interactions extending beyond a hard core.On leave from: Katedra Fizyki, Uniwersytetu Szczecinskiego, 70-451 Szczecin, Poland.     

Development in Synthesis,Electrochemistry, LB Moieties of Phenothiazine Based Units

A convenient and higher yielding synthetic route to N‐alkyl‐bis(thiophene)phenothiazine derivatives is reported and their aggregation, electrochemical properties and polymerization are characterized. The key step in the synthesis of this group of compounds has been the Stille type coupling reaction between the N‐alkyldibromophenothiazine and tin derivatives of thiophene as the best way for preparation of conjugated N‐alkylphenothiazine derivatives. For this group of compounds we also present an electrochemical polymerization effect and widely adopted approach to prepare structurally ordered thin, electroconducting films by Langmuir–Blodgett technique.     

New fluorescence probes for monitoring the kinetics of laser-initiated polymerization

Several new fluorescence probes useful for following photopolymerization have been characterized. Among these are probes which can be used in rapidly gelling monomer mixtures and for photochemical polymerization initiated by very high laser powers. Systems which can be used with polyolacrylates and either with visible initiators or with UV initiators are reported. © 1993 John Wiley & Sons, Inc.     

Time Consistent Dynamic Risk Measures

We introduce the time-consistency concept that is inspired by the so-called “principle of optimality” of dynamic programming and demonstrate – via an example – that the conditional value-at-risk (CVaR) need not be time-consistent in a multi-stage case. Then, we give the formulation of the target-percentile risk measure which is time-consistent and hence more suitable in the multi-stage investment context. Finally, we also generalize the value-at-risk and CVaR to multi-stage risk measures based on the theory and structure of the target-percentile risk measure.     

Directed and elliptic flow in 197Au+197Au at intermediate energies

Directed and elliptic flow for the ¹⁹⁷Au+¹⁹⁷Au system at incident energies between 40 and 150 MeV per nucleon has been measured using the INDRA 4π multi-detector. For semi-central collisions, the excitation function of elliptic flow shows a transition from in-plane to out-of-plane emission at around 100 MeV per nucleon. The directed flow changes sign at a bombarding energy between 50 and 60 MeV per nucleon and remains negative at lower energies. Molecular dynamics calculations (CHIMERA) indicate sensitivity of the global squeeze-out transition on the σ _NN and demonstrate the importance of angular momentum conservation in transport codes at low energies.