Semiempirical studies of core electron binding energy shifts: Part 5. SCC—MO investigation of keto—enol tautomerism in some 1,3-diketones and related anhydrides

The keto—enol tautomerism in malonaldehyde and some related 1,3-diketones is thoroughly discussed by the calculation of inner-core binding energies. The semiempirical wave-functions were obtained by the self-consistent charge (SCC—MO) molecular orbital procedure. The calculated O(1s) binding energies are generally in good agreement with available experimental data. The discrepancy found for the alcohol-type oxygen in acetylacetone is so large that it strongly indicates an error in experimental assignment. The calculations also provide conclusive evidence that enol-forms possess asymmetric hydrogen-bonded protons.     

Halogen adsorption on Fe(100): I. The adsorption of Cl2 studied by AES,LEED, work function change and thermal desorption

The initial sticking probability of chlorine on Fe(100) at room temperature is calculated to be 0.13, and there is evidence to suggest that the chlorine adsorbs into a short lived mobile precursor state above the surface. The work function change, Δφ, is proportional to coverage and reaches a maximum value of 1.43 eV at saturation. At this coverage a c(2 × 4) LEED pattern is formed. On heating, chlorine is lost from the surface, but the mechanism is such that no detectable loss is incurred at a constant elevated temperature. The c(2 × 4) pattern is shown to be a coincidence structure formed from a $\text{(}\text{1}\text{2}\text{3}\text{?1}\text{2}\text{3}\text{)}$ net of chlorine atoms on the Fe(100) substrate. This structure is a special case of the more general $\text{(}\text{1}\text{2}\text{tan}\text{α}\text{?1}\text{2}\text{tan}\text{α}\text{)}$ structure formed at lower concentrations of chlorine. The c(2 × 4) is formed when α = 56.31°, which gives the chlorine atoms a hard sphere diameter of 0.345 nm and a concentration of 0.75 atoms per four-fold site.     

On the dynamic form factor of an electron liquid

The mean field theories of an electron liquid at metallic densities, which go beyond the RPA, and which have been fairly successful so far, are shown to be inadequate when tested against phenomena involving high frequencies. It is also shown that by making a simple Gaussian ansatz for the imaginery part of the response function, χ″(q,ω), and using the zeroth, the first and the third frequency moments of density spectral function to determine the unknown parameters in χ″(q,ω), it is possible to understand at least semiquantitatively the available experimental information regarding the dynamic form factor. Implications of the present analysis as regards the further refinement of the present theories are indicated.     

Photoelectron asymmetries and two-electron satellites near the 3p → 3d giant-resonance region in atomic Mn

The partial cross-sections and photoelectron angular distributions for several lines in atomic Mn have been measured at photon energies between 50 and 72eV. The intensities of the 3d correlation satellites at 24–26 eV binding energy behave similarly to the mainline intensity near the 3p → 3d giant resonance, but show an enhancement near the 3p threshold which is not present for the main line. A configuration-interaction analysis is applied to help identify the origins of the satellites. The 3p/3d branching ratio from 55–72eV and the shape of the 3d cross section in the resonance region are in good agreement with many-body perturbation-theory calculations.     

Optical dephasing in a glass-like system: a photon echo study of pentacene in benzoic acid

Optical absorption and picosecond photon echo experiments are used to study the dephasing of pentacene in benzoic acid. It is shown that, while the absorption spectrum of pentacene is effected by proton transfer in the benzoic acid dimer, the dephasing is caused by elastic and inelastic phonon scattering processes.     

Picosecond rotational diffusion by differential single-photon fluorescence spectroscopy

The rotational diffusion contants of rhodamine-6G, coumarin-1 and N-acetyltryptophanamide in various solvents have been determined by an experimental method where the vertically and horizontally polarized fluorescence spectra are measured simultaneously by the same detector. The results indicate that the Debye—Stokes—Einstein model does not hold for coumarin-1 and N-acetyltryptophanamide in ethylene glycol.     

Molecular emission cavity analysis13-a new flame analytical technique : Part II.The determination of selenium and tellurium

The determination of 0.4–4 μg of selenium by molecular emission cavity analysis is described. Selenium in organic compounds is determined after oxygen flask combustion. Metal ion interferences are eliminated by reduction of selenium to the element, filtration onto a glass-fibre paper, and direct incorporation of the filter into the cavity. Applications to the determination of selenium in inorganic and organic compounds are described. The determination of μg-amounts of tellurium is also outlined.     

Evidence for a Ag adatom-molecule complex in surface enhanced raman scattering

The SERS spectrum of molecules adsorbed on Ag sols show, lines, in the 200–300 cm^?1 region in the absence of Cl^? ions These lines are attributed to a Ag-N complex and frequency calculations show that they correspond to the vibrations of the molecule bound to a single silver atom.