Structure and dynamics of olefin radical cation aggregates. Time-resolved fluorescence detected magnetic resonance

Journal Article · Thu Apr 10 04:00:00 EST 1986 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100399a021· OSTI ID:6035437

Desrosiers, M F; Trifunac, A D

The time-resolved EPR spectra and thus the structure and dynamics of transient hydrocarbon radical cations are obtained by the pulse radiolysis-fluorescence detected magnetic resonance (FDMR) technique. Here the authors report the observation of short-lived radical cations from olefins. FDMR-EPR spectra of radical cations from tetramethylethylene and cyclohexadiene are illustrated. The olefin radical cations, FDMR spectra are concentration-dependent, since dimerization with neutral molecules takes place at higher (>10/sup -2/ M) olefin concentration. Rate constants for the dimerization reaction are derived and the effect of solvent viscosity on aggregate formation is demonstrated. By monitoring the further reactions of dimer cations the authors have obtained EPR evidence for previously unobserved higher-order (multimer) radical cation aggregates of olefins. 16 references, 5 figures.

• Research Organization: Argonne National Lab., IL
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 6035437
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:8; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ALKENES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
FLUORESCENCE
HYDROCARBONS
INFORMATION
ION PAIRS
LUMINESCENCE
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
PULSE TECHNIQUES
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
REACTION INTERMEDIATES
RESONANCE
STRUCTURAL CHEMICAL ANALYSIS