Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Electron spin resonance spectroscopic studies of radical cation reactions

Thesis/Dissertation ·
OSTI ID:7233039
A spin Hamiltonian suitable for theoretical analyses of ESR spectra is derived using the general effective Hamiltonian theory in the usual Schroedinger representation. The Permutation Indices method is extended to obtain the dynamic exchange equations used in ESR lineshape simulation. The correlation between [beta]-hydrogen coupling constants and their geometric orientations are derived using a perturbation method. The three electron bond model is extended to rationalize unimolecular rearrangements of radical cations. The ring-closed radical cations of 9,10-octalin oxide and synsesquinorbornene oxide have been characterized by ESR spectroscopy in the CFCl[sub 3] matrix at low temperature. The self-electron-transfer rate constants between the methyl viologen dication and cation have been determined by dynamic ESR lineshape simulations at room temperature in allyl alcohol, water, methanol and propargyl alcohol solvents. The radical cation formed by the radiolytic oxidation of allylamine in Freon matrices at 77 K is the 3-iminiopropyl distonic species(3-iminium-1-propyl radical). The nucleophilic endocylization of the but-3-en-1-ol radical cation to the protonated tetrahydrofuran-3-yl radical was observed in the radiolytic oxidation of but-3-en-1-ol in Freon matrices. ESR studies of the radiolytic oxidation of 1,5-hexdiyne have resulted in characterization the 1,5-hexadiyne radical cation isomerizing to the 1,2,4,5-hexatetraene radical cation. The symmetric (C[sub 2v]) bicyclo[3.3.0]-octa-2,6-diene-4,8-diyl(a bridged 1,4-bishomobenzene species) radical cation is produced by the radiolytic oxidation of semibullvalene in Freon matrices. The ring-opening 3,4-dimethylenecyclobutene radical cation to 1,2,4,5-hexatetraene radical cation was observed in the photolysis of 3,4-dimethylenecyclobutene radical cation. The cyclooctatetraene radical cation generated by radiolytic oxidation photoisomerizes to bicyclo[3.3.0]octa-2,6-diene-4,8-diyl radical cation.
Research Organization:
Tennessee Univ., Knoxville, TN (United States)
OSTI ID:
7233039
Country of Publication:
United States
Language:
English

Similar Records

Electron spin resonance evidence for the 1,4-bishomobenzene structure of the C sub 2. nu. ring-opened semibullvalene (bicyclo(3. 3. 0)octa-2,6-diene-4,8-diyl) radical cation
Journal Article · Tue Mar 27 23:00:00 EST 1990 · Journal of the American Chemical Society; (USA) · OSTI ID:6518908
Electronic structure and photochemical interconversions of dihydropentalene radical cations
Journal Article · Wed Aug 02 00:00:00 EDT 1995 · Journal of the American Chemical Society · OSTI ID:111187
Photoinduced electrocyclic 1,5-closure of the cyclooctatetraene radical cation to a bridged 1,4-bishomobenzene (bicyclo(3. 3. 0)octa-2,6-diene-4,8-diyl) radical cation
Journal Article · Tue Mar 27 23:00:00 EST 1990 · Journal of the American Chemical Society; (USA) · OSTI ID:6518473

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400200 -- Inorganic
Organic
& Physical Chemistry
664200* -- Spectra of Atoms & Molecules & their Interactions with Photons-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ALKENES
ALKYL RADICALS
CATIONS
CHARGED PARTICLES
CHEMICAL REACTIONS
CYCLOALKENES
ELECTRON SPIN RESONANCE
FREONS
HALOGENATED ALIPHATIC HYDROCARBONS
HAMILTONIANS
HYDROCARBONS
IONS
MAGNETIC RESONANCE
MATHEMATICAL OPERATORS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PROPYL RADICALS
QUANTUM OPERATORS
RADICALS
RESONANCE