Zur Photochemie von Allylaryläthern. 55. Mitteilung über Photoreaktionen

The photochemical reactions of different allyl aryl ethers (Scheme 3) were investigated in hydrocarbons (Chap. 3.1) and in alcoholic solvents (Chap. 3.2). The composition of the photoproducts depended very much on the nature of the solvent. Irradiation (3–95 h) of different methyl substituted allyl aryl ethers ( 1, 3, 5, 7 and 11 ) with a low pressure mercury lamp (λ_Emiss. = 254 nm; 6 or 15 Watt) under argon (quartz vessel) resulted in the formation of 2-, 3– and 4-substituted phenols, dienones and products of consecutive reactions (Tables 1–4 and 6). The results suggested that all products were formed by homolytic cleavage of the C? O bond in the singlet state of the ethers to intermediate radical-geminates (Scheme 5) followed by radical recombination of the two fragments. No products were formed by concerted processes (Table 5, Schemes 5 and 6). Upon irradiation of allyl aryl ethers lacking alkyl substituents at position 4 ( 1 and 5 ) in protic solvents, mainly 2- and 4-allylated phenols were obtained (Tables 1 and 4); 3-allylated phenols were formed only in small amounts (0.02%). However, in aromatic hydrocarbons or cyclohexane 3-allylated phenols were obtained from 1 , 5 and 11 in significant amounts (3–11%; Tables 1, 4 and 6). E.g., upon irradiation of allyl-2,6-dimethyl-2,4-cyclohexadien-1-one ( 6 ) besides 3- and 4-allyl-2, 6-dimethyl-phenol ( 23 and 24 ). Irradiation of 5 in methanol afforded 23 and 6 only in traces, whereas 24 was the main product.     

A note on the importance of d orbitals in the calculation of effective interactions and the excitation spectra of atoms and molecules

The focal point of our discussion is the examination of truncated basis sets used in obtaining an accurate first principles clculation of the effective valence shell Hamiltonian by the canonical transformation-cluster expansion approasch. Subsequent diagonalization of this effecitve valence shell hamiltonian yields the valence shell transition energies. A detailed analysis of numerical results obtained using a number of different basis sets of hydrogen-like orbitals together with rigorous symmetry arguments celarly demonstrates the special role played by d orbitals in computing the ³P → ¹D transition energy in carbon. The failure of early attempts to calculate the effective Hamiltonian for ethylene from first principles is examined in the light of recent ab initio calculations on ethylene involving d orbitals and the computations reported in this paper. We conclude that accurate calculations of the effective valence shell Hamiltonian for molecules must consider d orbitals in the excited orbital basis set.     

Heats of adsorption of linear CO species adsorbed on the Au degrees and Ti+delta sites of a 1% Au/TiO2 catalyst using in situ FTIR spectroscopy under adsorption equilibrium

The heats of adsorption of two linear CO species adsorbed on the Au degrees particles (denoted L(Au degrees)) and on the Ti(+delta) sites (denoted L(Ti+delta)) of a 1% Au/TiO(2) catalyst are determined as the function of their respective coverage by using the AEIR procedure (adsorption equilibrium infrared spectroscopy) previously developed. Mainly, the evolutions of the IR band area of each adsorbed species (2184 cm(-1) for L(Ti+delta) and at 2110 cm(-1) for L(Au degrees)) as a function of the adsorption temperature T(a), at a constant CO adsorption pressure P(CO), provide the evolutions of the coverages theta(LTi+delta) and theta(LAu degrees ) of each adsorbed CO species with T(a) in isobar conditions that give the individual heats of adsorption. It is shown that they linearly vary from 74 to 47 kJ/mol for L(Au degrees ) and from 50 to 40 kJ/mol for L(Ti+delta) at coverages 0 and 1, respectively. These values are consistent with literature data on model Au particles and TiO(2). In particular, it is shown that the mathematical formalism supporting the AEIR procedure can be applied to literature data on Au-containing solids (single crystals and model particles).     

Universal variable length coding for an integrated approach to image coding

We propose a new entropy coding scheme, denoted in this paper as the UVLC (universal variable length coding). It is universal in the sense that its efficiency is close to one for a large class of images. The UVLC, when it is applied to block orthogonal transforms, processes groups of blocks at the bit level, using universal codes designed for binary memoryless sources. It can be used for every video coding application, from high definition TV (HDTV) to high quality videotelephony (above 2 Mbit/s) for transform or subband coding. Last but not least, its implementation is very regular and can be realized in a single chip for the encoding oftv at theccir 601 format.     

Periodic solutions of dry friction problems

Dry friction problems lead to discontinuous differential equations, e.g. to

Measurement of γp→K + Λ and γp→K + Σ 0 at photon energies up to 1.47 GeV

The reactions pK ⁺ and pK ^{+ 0} have been measured with the multiparticle detector system SAPHIR at ELSA in Bonn. Besides the differential cross sections the polarization and, for the first time, the ⁰ polarization have been determined in a photon induced reaction. All data are presented as functions of the photon energy (from threshold up to 1.47 GeV) and of the kaon production angle (0°–180°). The polarization of both and ⁰ is substantial at all energies and varies strongly with the production angle.This work is supported by the Bundesminister für Forschung und Technologie (BMFT), FK 06 BN 621 I     

Level crossing resonance due to chlorine nuclei in a free radical

Muonium adds to allyl chloride, CH₂=CHCH₂Cl, to form two radicals: MuCH₂CHCH₂Cl (main product) and CH₂CHMuCH₂Cl (minor product). Both radicals were fully characterized bySR andLCR. In the main product, the LCR lines due to the³⁵Cl and³⁷Cl nuclei were observed. Also, the temperature dependence of various hyperfine coupling constants (hfc) indicates that both Mu and Cl eclipse the unpaired electronp ₂-orbital in the minimum energy conformation. For the fragment-CH₂Cl, the presence of Mu in the-position is found to affect significantly the hfc of Cl in the-position; an internal rotational barrier of 12 kJ mol^–1 was estimated using a simpleV ₂ torsional potential.