Charge transfer band of the benzyl radical--halide ion formed by dissociative electron attachment to benzyl halides in a rigid organic matrix

Journal Article · Thu Aug 26 04:00:00 EDT 1976 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100559a012· OSTI ID:7353294

Irie, M; Shimizu, M; Yoshida, H

In order to elucidate the anomalous features previously reported on electronic spectra of the benzyl radical generated from benzyl chloride, the spectra were studied by the fluorescence spectrophotometric method for benzyl radicals generated from benzyl fluoride, chloride, bromide, and iodide in a 3-methylhexane matrix by either uv or ..gamma.. irradiation at 77/sup 0/K. When benzyl radicals were generated by dissociative electron attachment to the benzyl halides in the ..gamma..-irradiated matrix, the halide ions close to the benzyl radicals were found to cause a red-shift of the spectra of the radicals, a change in the vibrational structure (especially an increase in the 0 to 0 band intensity of the fluorescence spectrum), and also the appearance of CT bands due to complexes between the halide ion and the benzyl radical at 265, 362, 413 and 500 nm for F/sup -/, Cl/sup -/, Br/sup -/, and I/sup -/, respectively. The dependence of the CT transition energy upon the halide ions agrees well with that expected from the ionization energy of the donors (the electron affinity of the halogen atoms) and the solvation energy of the halide ions in the matrix. For the benzyl radical from benzyl chloride, the effects of the chloride ion were found to be much less in 2-methyltetrahydrofuran matrix, and could not be observed at all in an ethanol matrix. Halide ions also caused a decrease in the fluorescence lifetime of the benzyl radical.

• Research Organization: Hokkaido Univ., Sapporo
• OSTI ID: 7353294
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 80:18; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ALCOHOLS
ANIONS
AROMATICS
ARYL RADICALS
BEAMS
BENZYL RADICALS
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHEMISTRY
DECOMPOSITION
ELECTROMAGNETIC RADIATION
EMISSION SPECTRA
ETHANOL
FLUORESCENCE
FURANS
GAMMA RADIATION
GLASS
HALIDES
HALOGEN COMPOUNDS
HALOGENATED AROMATIC HYDROCARBONS
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
IONIZING RADIATIONS
IONS
LIFETIME
LOW TEMPERATURE
LUMINESCENCE
MTHF
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PHOTON BEAMS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
RADIOLYSIS
SPECTRA
ULTRAVIOLET RADIATION
YIELDS