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Ab initio molecular orbital calculations for the energy and intensity of X-ray transitions associated with the carbon monoxide, hydrogen cyanide and carbon dioxide molecules have been calculated at the Hartree-Fock level. It is demonstrated that in general the absolute transition probabilities are sensitive to the inclusion of electronic relaxation effects and interatomic transition moment contributions. It is concluded that calculations for molecular X-r!ly emission henomena should be undertaken at least at the multicentre relaxed Hartree-Fock level to achieve a realistic basis for comparison with experiment. Total carbon-K X-ray rates do not show a strong variation with changes in the molecular environment. The total rates are of a similar magnitude to those reported for the atom. The calculated carbon-K fluorescence yield is also similar in both the carbon atom and the CO2 molecule.

Some basic thermodynamic parameters such as Gibbs free energies, enthalpies of reactions and equilibrium compositions of products from the pyrolysis and partial oxidation of methane to higher hydrocarbons in the gas phase have been determined within a consistent framework for the temperature range 800-1500 K and the pressure range 0.1-3 MPa, by using the CSIRO-SGTE THERMODATA system.' It has been established that the pyrolysis of methane to higher hydrocarbons, e.g. acetylene, ethylene, ethane, prop-1-ene, propane, benzene, toluene, naphthalene, 1-methylnaphthalene and 2-methylnaphthalene, considered as separate reactions, is a highly endothermic reaction with the Gibbs free energies for the individual reactions being positive until 1300 K. The aromatics are thermodynamically most favoured with the equilibrium yields increasing with temperature. Addition of 0 2 lowers the heats of synthesis and the free energies for methane conversion but no enhancement in the equilibrium yields of hydrocarbons is observed. When solid carbon is allowed, it is the dominant product in all cases with the equilibrium yields for all hydrocarbons becoming negligible. Increasing the pressure at a particular temperature has more effect on the lowering of the equilibrium conversion of methane than on the suppression of solid carbon. Such data are valuable for understanding the conversion limits for methane into higher hydrocarbons.

The theory of lineshapes of satellites in photoelectron spectra in a simplified fourth-order perturbation theory is developed. The calculation of the monopole satellites of the 2p ionization of the neon atom has been carried out in second- and simplified fourth-order perturbation theory. The theoretical linewidths and the relative intensities of the satellites are in agreement with experimental photoelectron spectra taken at h nu =130.1 eV.