Solvation of benzophenone anion radical in ethanol and ethanol/2-methyltetrahydrofuran mixture
The electron spin-echo modulations and the absoprtion spectra of benzophenone anion radicals generated by ..gamma..-irradiation in the glassy matrices of ethanol and ethanol2-methyltetrahydrofuran mixtures have been measured for elucidating the mechanism of spectral shift observed during the solvation of the anion radicals in alcohols. The anion radical generated at 4.2 K in the ethanol matrix maintains the same solvation structure as that of neutral benzophenone. At 77 K ethanol molecules solvate the anion radical by orienting the O-H dipoles toward the anion radical. The anion radical is hydrogen-bonded by two ethanol molecules through the p/sub z/ orbital on the benzophenone oxygen which composes the ..pi.. orbitals of anion radical. Three kinds of anion radicals are observed in the mixed matrix at 77 K. Two of them are essentially the same as those observed in the ethanol matrix at 4.2 and 77 K. The third has the absorption maximum at 700 nm and is attributed to the anion radical hydrogen-bonded by one ethanol molecule through the p/sub z/ orbital. It is concluded that the spectral shift observed in alcohols is caused by the stabilization of a SOMO ..pi..* orbital induced by the hydrogen bonding with the (RO)H--O--H(OR) angle perpendicular to the molecular plane of the anion radical
- Research Organization:
- Hokkaido Univ., Sapporo, Japan
- OSTI ID:
- 5248634
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 92:2
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
BENZOPHENONE
RADIOLYSIS
ETHANOL
MTHF
ABSORPTION SPECTROSCOPY
ACOUSTIC ESR
ANIONS
EXPERIMENTAL DATA
RADICALS
ULTRALOW TEMPERATURE
VERY LOW TEMPERATURE
VISIBLE SPECTRA
ALCOHOLS
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
ELECTRON SPIN RESONANCE
FURANS
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
IONS
KETONES
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RESONANCE
SPECTRA
SPECTROSCOPY
TETRAHYDROFURAN
400600* - Radiation Chemistry