Radical pair formation in. gamma. -irradiated 2-methyltetrahydrofuran rigid solutions of polynitrobenzenes
The ..gamma..-irradiated MTHF (2-methyltetrahydrofuran) rigid solutions of mDNB (m-dinitrobenzene) and sTNB (s-trinitrobenzene) showed at 77 K ESR spectra characteristic of triplet species in addition to the spectra of doublet species, whereas no triplet ESR spectra were observed for the mononitrobenzene and o- and p-di-nitrobenzene solutions. The distances of the unpaired spins evaluated from the observed fine structure constants by using a point-dipole approximation are 4.3 and 4.6 A for the mDNB solution and 3.9 and 4.7 A for the sTNB solution. The detection of only the solute anion radicals by the optical absorption spectra of the irradiated solutions and the difference of the rate of formation for the triplet species and the solute anion strongly suggest that the triplet species are ascribed to the solute anion-solvent radical pairs. Such radical pairs are most likely to be formed through the migration of a MTHF cation radical, i.e., so-called hole migration, to a specific site between the two nitro groups on the meta positions of a solute anion followed by the production of a stable solvent radical, which is paired with the solute anion.
- Research Organization:
- Inst. of Physical and Chemical Research, Wako, Japan
- OSTI ID:
- 6205485
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 85:12; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400600* -- Radiation Chemistry
ANIONS
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
FURANS
GAMMA RADIATION
HETEROCYCLIC COMPOUNDS
IONIZING RADIATIONS
IONS
LOW TEMPERATURE
MAGNETIC RESONANCE
MTHF
MULTIPLETS
NITRO COMPOUNDS
NITROBENZENE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
RADIOLYSIS
RESONANCE
TETRAHYDROFURAN
TRIPLETS