Optical absorption spectra of localized electrons generated at 1. 6 K in polar matrices: Evidence for presolvated electrons

Journal Article · Thu Mar 15 04:00:00 EST 1979 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.437845· OSTI ID:6269348

Dolivo, G; Kevan, L

Glassy samples of ethanol, methanol +5 mol % water, 10 M and 18 M NaOH in H/sub 2/O, 5 M K/sub 2/CO/sub 3/ and 7 M NaClO/sub 4/ in D/sub 2/O were x irradiated at 1.6 K. After irradiation the optical absorption spectra of the localized electrons generated were recorded at 1.6 K. Red shifts relative to spectra after irradiation at 4.2 K were observed in all matrices indicating stabilization of some presolvated electrons characterized by a nonequilibrium first solvation shell. Particularly in deuterated matrices, where observation further into the infrared is possible, a long infrared tail assigned to presolvated electrons is detected at 1.6 K; these infrared tails are not stabilized at 4.2 K. Analysis of the spectral shifts after irradiation at 77, 4.2, and 1.6 K indicates that an increasingly larger population of presolvated electrons is stabilized as the temperature is lowered and that a parallelism for electron solvation exists in all the matrices studied including ethanol. In the methanol and aqueous matrices, electron solvation is much more efficient than in ethanol, and the predominant population of localized electrons is largely solvated even at 1.6 K. The spectral shifts in 18 M NaOH glasses are also consistently interpreted in terms of presolvated electron stabilization and do not require postulation of (Na/sup +/--e/sup -/) pair stabilization as suggested in earlier work at 77 K.

• Research Organization: Department of Chemistry, Wayne State University, Detroit, Michigan 48202
• OSTI ID: 6269348
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 70:6; ISSN JCPSA
• Country of Publication: United States
• Language: English

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71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
ABSORPTION SPECTRA
ALCOHOLS
DATA
DATA FORMS
DEUTERIUM
ELECTRONS
ELEMENTARY PARTICLES
ETHANOL
EXPERIMENTAL DATA
FERMIONS
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
INFORMATION
IRRADIATION
ISOLATED VALUES
ISOTOPES
LEPTONS
LIGHT NUCLEI
METHANOL
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
SOLVATED ELECTRONS
SPECTRA
STABLE ISOTOPES
ULTRALOW TEMPERATURE
VERY LOW TEMPERATURE