Dynamic spectral shifts of molecular anions in organic glasses. [Pulse radiolysis]
Time-dependent spectra of the radical anions of pyromellitic dianhydride and p-dinitrobenzene have been observed after formation by pulse radiolysis in frozen 2-methyltetrahydrofuran and triacetin glasses. At temperatures near the glass transition, the spectra shift toward the blue over the entire observed time range 100 ns to 100 s), while at temperatures well below the glass transition, the spectral shifts can be stopped or greatly slowed. The magnitudes of the shifts are not large (typically approx. = to 10 nm), but because they are larger than the vibrational line widths, dramatic kinetics may be observed: the absorbance grows or decays by more than a factor of five at some wavelengths. The observations are consistent with a solvent molecule reorientation mechanism for spectral shifts of molecular ions in low-temperature organic glasses. 6 figures.
- Research Organization:
- Argonne National Lab., IL
- DOE Contract Number:
- W-31-109-ENG-38
- OSTI ID:
- 6731608
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 86:13
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ACETIC ACID ESTERS
RADIOLYSIS
ANHYDRIDES
CHEMICAL REACTION YIELD
MTHF
NITRO COMPOUNDS
ABSORPTION SPECTRA
ANIONS
AROMATICS
CHEMICAL REACTION KINETICS
ELECTRONIC STRUCTURE
ETHANOL
EXPERIMENTAL DATA
LOW TEMPERATURE
MATRIX ISOLATION
MOLECULAR STRUCTURE
ORGANIC SOLVENTS
PULSED IRRADIATION
RADICALS
SPECTRAL SHIFT
STRUCTURAL CHEMICAL ANALYSIS
TEMPERATURE DEPENDENCE
TIME DEPENDENCE
ALCOHOLS
CARBOXYLIC ACID ESTERS
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
ESTERS
FURANS
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
IONS
IRRADIATION
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
REACTION KINETICS
SOLVENTS
SPECTRA
TETRAHYDROFURAN
YIELDS
400600* - Radiation Chemistry