Unimolecular Fragmentation of Energy Selected Allene Molecular Cations

The unimolecular fragmentations of internal energy selected allene molecular ions ( 1 ⁺) have been investigated by photoelectron-photoion coincidence spectroscopy. The energy dependence of the branching ratio between the two most important fragmentation channels is reported, together with values for the kinetic energy release during fragmentation. Loss of an hydrogen atom from 1 ⁺ is interpreted to proceed via two paths, yielding different isomeric forms of C₃H with different kinetic energy release values.     

Pulsradiolytische Untersuchungen der Reaktion des e aq − mit halogenierten aromatischen Verbindungen

Kinetic pulse radiolysis experiments (1 s pulse duration) on the reaction of e _aq ^– with halogenated aromatic compounds (fluoro-, chloro-, bromobenzene, benzylchloride and phenethylchloride were carried out in order to check the existence and to investigate the fate of an electron adduct. The measured absorption spectra, being identical with those previously observed for the phenyl and benzyl radical, and thepH dependence of the formation of the H-adducts, indicating no protonation of an intermediateRX ^–, can be explained simply by quantitative elimination of the halide. No evidence for the existence of an electron adduct as an intermediate could be obtained under the applied experimental conditions.

     

Linear dichroism and magnetic circular dichroism of acenaphth[1,2-a]acenaphthylene

Ultraviolet-visible polarized absorption spectra of acenaphth[1,2-a]acenaphthylene have been determined from low-temperature measurements of linear dichroism in stretched polyethylene. The magnetic circular dichroic spectrum has been measured in solution. Transition energies, polarizations, and relative intensities, as well as the absolute signs of B terms of low-energy transitions are in good agreement with results of π-electron calculations and with simple qualitative arguments, which also account for the close similarity to the known spectra of acenaphthylene.