Study of radical ions in the condensed phase by fluorescence-detected magnetic resonance. [Electron beams]

Journal Article · Thu May 02 04:00:00 EDT 1991 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100162a007· OSTI ID:5973125

Werst, D W; Trifunac, A D ^[1]

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1. Argonne National Lab., IL (United States)

Magnetic resonance studies of transient condensed-phase radical ions have been realized for the first time without the use of a stabilizing matrix. The occurrence, structure, and reactivity of radical cations and radical anions in the condensed phase using time-resolved fluorescence-detected magnetic resonance (FDMR) is reviewed. FDMR observes the time-resolved EPR spectra of spin-correlated radical-ion pairs on the 10{sup {minus}8}-10{sup {minus}6} time scale. FDMR studies have elucidated the identity and fate of primary radical cations in saturated hydrocarbons, alcohols, and other solvent media exposed to ionizing or photoionizing radiation. In photoionization, FDMR allows the determination of the photophysical pathway, i.e., the photon order and the multiplicity of the state which is ionized. The formation of secondary radical cations via electron transfer from solutes to solvent radical cations allows the FDMR/pulse radiolysis method to study a wide range of organic radical cations. Radical-cation reactions that have been studied include unimolecular dissociation, charge transfer, aggregate formation, and ion-molecule reactions. Ion-molecule reactions such as proton transfer are the principal channels besides neutralization for radical-cation decay in the condensed phase.

• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 5973125
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 95:9; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400500 -- Photochemistry
400600* -- Radiation Chemistry
ALKANES
ALKENES
AMINES
ANIONS
BEAMS
CATIONS
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ELECTRON BEAMS
ELECTRON SPIN RESONANCE
ELECTRON TRANSFER
EMISSION SPECTROSCOPY
EXPERIMENTAL DATA
FLUORESCENCE SPECTROSCOPY
HYDROCARBONS
INFORMATION
IONIZATION
IONS
LASER RADIATION
LEPTON BEAMS
LIFETIME
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PARTICLE BEAMS
PERFORMANCE
PHOTOIONIZATION
RADIATION EFFECTS
RADIATIONS
RADICALS
RADIOLYSIS
RESOLUTION
RESONANCE
SOLVENTS
SPECTROSCOPY
TIME DEPENDENCE
TIME RESOLUTION
TIMING PROPERTIES
ULTRAVIOLET RADIATION