Lattice-dynamical calculations for fluorene,carbazole, dibenzofuran and dibenzothiophen

For crystalline fluorene, carbazole, dibenzofuran and dibenzothiophen several properties have been calculated using semi-empirical atom-atom potentials Calculated geometrical parameters, Raman-active lattice frequencies, enthalpies of sublimation and crystallographic temperature factors agree with observed values. However, except for dibenzothiophen, infrared-active lattice frequencies are not consistent with any potential so far tried     

F?F coupling constants in dichlorotetrafluorocyclopropanes

The ¹⁹F NMR spectra of the cis- ( 1 ) and the trans-isomer ( 2 ) of the 1,2-dichlorotetrafluorocyclopropane and that of the 1,1-dichlorotetrafluorocyclopropane ( 3 ) have been investigated at different temperatures and in several solvents. From chemical shift calculations the two geminal fluorines in the cis-isomer ( 1 ) could be assigned and on this basis the two vicinal coupling constants of 1 , J_trans (ca. 140°) and J_cis (ca. 0°), were unequivocally distinguished. By frequency sweep double resonance J_trans has been shown to be of opposite sign to J_gem, whereas for J_cis the situation has been found to be reversed. Therefore J_trans is presumably negative and J_cis positive. Only the N(J_cis + J_trans) value could be extracted from the vicinal coupling constant in the fragment ? CFCl? CFCl? could be evaluated. It has been noted that J_cis is more sensitive to changes in temperature than is J_trans. The variations of J_cis and J_trans induced by solvents are, on the contrary, small and irregular and no correlation with the dielectric constant of the medium has been noted. The different temperature dependence of J_cis and J_trans can be useful for assigning the vicinal F? F coupling constants in cyclopropane derivatives and also for defining their signs. This method was applied to the coupling constants extracted from the ¹³C satellite spectrum of isomer 3 . The coupling constants results were compared with some literature data already known, and some rationalisation and correlations from the trends was attempted.     

An extended hückel study of adsorption of acetylene on Pt(111)

The parameterization of Extended Hückel MO Theory for the study of the interactions between hydrocarbons and Pt is analysed in detail. Single-ζ and double-ζ d functions of variable diffuseness are tested. The stability of acetylene and many molecular fragments and atoms on the surface is discussed in terms of binding energies and hydrocarbon—surface bond stretching force constants. Pt…H non-bonded repulsions are seen to be relevant, and a formula is proposed to describe these interactions. The metal is shown to offer a large catalytic effect in the reactions of rearrangement of acetylene, and, depending on the temperature and the availability of free hydrogen, H₃CC or H₃CCH are shown to be the most likely surface species. The geometries of adsorption compare rather favourably with LEED intensity studies. The use of EHT in the calculation of density of states curves and electronic spectra is discussed.     

The structure of hydrogen adsorbed on Ni(111) at low temperature by leed intensity analysis

Observed and calculated LEED intensity spectra for the p(2 × 2) pattern given by the adsorption of hydrogen on Ni(111) at 173 K are reported. Among the several model geometries tried that with the hydrogen atoms adsorbed in one of the two possible hollow sites seems to be the most probable.     

19F NMR analysis of the fluorides of perfluorocyclohexane-sulphonic acid and of 3-trifluoromethylperfluorocyclopentane-1-sulphonic acid

From the electrochemical fluorination of the chloride and the fluoride of benzenesulphonic acid, in addition to the main product C₆F₁₁SO₂F, the side products C₅F₈(CF₃)SO₂F, a structural isomer of the main product and C₆F₁₀Cl? SO₂F are also obtained. The NMR analysis of these products was performed. Chemical shift and coupling constant values were obtained for all the compounds. The NMR parameters of the main product are compared with those of perfluoromethylcyclohexane according to the data of Jolley, Sutcliffe and Walker. From the NMR parameters of C₅F₈(CF₃)SO₂F it was possible to demonstrate that substitution on the ring for —SO₂F and CF₃— is of the 1,3 and not the 1,2 type.     

Contributions from higher twist effects to the quark fragmentation functions in neutrino data

Quark fragmentation functions are studied with ≈3500 charged current events induced in the bubble chamber Gargamelle by neutrinos of the SPS wide band beam, with 〈E_ν〉 ≈ 25 GeV. The Q² and W² regions covered by this experiment are Q² ≈ 0–40 GeV² and W² ≈ 1–100 GeV², the mean values being 〈Q²〉 = 6.5 GeV², 〈W²〉 = 22GeV². A correlation between the variables $\text{z =}\text{E}{}_{\mathrm{\pi }}\text{E}{}_{\mathrm{<mtext>H</mtext>}}$ and $\text{y =}\text{E}{}_{\mathrm{<mtext>H</mtext>}}\text{E}{}_{\mathrm{v}}$ is found in the data in the region Q² = 1–10 GeV², which can be explained in terms of higher twist effects. These effects reproduce the Q² evolution of the non-singlet moments of the fragmentation function without any need for logarithmic terms.     

Ab initio calculations including solvent effects of the structure of pyrazine, 4-nitropyridine and dicyanobenzenes ion pairs

The potential surfaces of pyrazine, 4-nitropyridine, 1,2-, 1,3-, 1,4- dicyanobenzene radical anions have been calculated within theab initio and electrostatic molecular potential formalism, including the effect of the solvent. These potential surfaces suggest models of ion pairs with alkali cations, which are in agreement with those deduced from related ESR spectra.     

Post-collision interactions in the (e,e′ Auger) coincidence spectra

Summary The argon LMM Auger energy spectra measured in a recent (e,e′ Auger) coincidence experiment are compared with the predictions of a semiclassical model of this post-collision interactions (PCI). The model satisfactorily reproduces both the measured shift towards higher energy and the observed lineshapes of the experimental spectra.