Palladium-catalyzed synthesis of substituted cyclopentadienes and indenes from allylic esters

Various mono- and di-substituted cyclopentadienes have been prepared by palladium-catalyzed alkylation of allylic esters with cyclopentadienide and t-butyl-cyclopentadienide anions. The same procedure has been applied to the preparation of substituted indenes.     

Higgs production and decay with a fourth Standard-Model-like fermion generation

State-of-the-art predictions for the Higgs-boson production cross section via gluon fusion and for all relevant Higgs-boson decay channels are presented in the presence of a fourth Standard-Model-like fermion generation. The qualitative features of the most important differences to the genuine Standard Model are pointed out, and the use of the available tools for the predictions is described. For a generic mass scale of 400−600 GeV in the fourth generation explicit numerical results for the cross section and decay widths are presented, revealing extremely large electroweak radiative corrections, e.g., to the cross section and the Higgs decay into WW or ZZ pairs, where they amount to about −50 % or more. This signals the onset of a non-perturbative regime due to the large Yukawa couplings in the fourth generation. An estimate of the respective large theoretical uncertainties is presented as well.     

Non-markovian effects in NMR relaxation processes: An application to molecular dynamics in branched and cross-linked solid polymers

The dynamic of restricted rotatranslation of mobile structural defects along a polymer chain are treated with an equation of motion with a non-Markovian, stochastic force. The MORI/KUBO/ZWANZIG representation gives a stochastic process with a memory where the loss of correlation is dependend on the restriction of diffusional motion of defects. The influence of crosslinks and branchings of the polymer chains on the molecular dynamics are discussed. The analytical spectral densities of ω^−-α-type characterized by the fractal dimensions of the relevant processes in the different polymeric systems, e. g. cis-polybutadiene, cis-polyisoprene, styrene-butadiene-rubber, high density and linear low density polyethylenes, are compared with the observed NMR data.     

A new algorithm to evaluate bielectronic integrals with 1s Slater‐type orbitals obtained by the integral transforms

This article presents a variation of the integral transform method to evaluate multicenter bielectronic integrals (12|34), with 1s Slater‐type orbitals. It is proved that it is possible to define, out of the expression of (12|34) given by the integral transform method, a function F(q) that has the property of having a unique Q, such that F(Q) = (12|34). Therefore, F(q) may be used to calculate (12|34). It is shown that the evaluation of F(Q) turns out to be simpler than the three‐dimensional integral involved in the calculation of (12|34), and an algorithm is presented to calculate Q. The results show that relative errors on the order of 10^?3 or lower are obtained very efficiently. In addition, it is shown that the proposed algorithm is very stable. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Rapid comprehensive characterization of crude oils by thermogravimetry coupled to fast modulated gas chromatography–single photon ionization time-of-flight mass spectrometry

Comprehensive multi-dimensional hyphenation of a thermogravimetry device (i.e. a thermobalance) to gas chromatography and single photon ionization–time-of-flight mass spectrometry (TG–GC×SPI–MS) has been used to investigate two crude oil samples of different geographical origin. The source of the applied vacuum ultraviolet radiation is an electron beam pumped rare gas excimer lamp (EBEL). The soft photoionization favors the formation of molecular ions. Introduction of a fast, rapidly modulated gas chromatographic separation step in comparison with solely TG–SPI–MS enables strongly enhanced detection especially with such highly complex organic matrices as crude oil. In contrast with former TG–SPI–MS measurements, separation and identification of overlying substances is possible because of different GC retention times. The specific contribution of isobaric compounds to one mass signal is determined for alkanes, naphthalenes, alkylated benzenes, and other compounds.

Relaxation of top mass limits in the two-Higgs-doublet model

The limits on the top quark mass from the recent measurement of the W and Z masses are analysed in the two-Higgs-doublet extension of the standard model. It is found that the addition of a second Higgs doublet relaxes the top mass limit considerably.