Primary reactions of localized electrons in rhamnose crystals studied by pulse radiolysis and ESR spectroscopy

Journal Article · Sat Nov 15 04:00:00 EST 1980 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.440014· OSTI ID:6903909

Samskog, P; Lund, A; Nilsson, G; Symons, M C.R.

The optical absorption spectrum of localized electrons in rhamnose crystals grown from H/sub 2/O and D/sub 2/O solutions has been obtained by means of pulse radiolysis. The absorption maximum is at 500 nm, the half-width is 250 nm, and epsilonG=9000 M/sup -1/ cm/sup -1/ (100 eV)/sup -1/ at 293 K. The decay is first order. The rate constants at 293 K and the activation energies are 6.9 x 10/sup 7/ s/sup -1/ and 4.1 kcal/mol in the protonated crystal and 4.3 x 10/sup 7/ s/sup -1/ and 5.4 kcal/mol in the deuterated crystal. The assignment of the optical spectrum has been made by ESR. In the deuterated crystal irradiated and measured at 67 K the electron is trapped and characterized by a single easily bleachable line with g<2.0023. The electron reacts thermally to form a hydroxy alkyl radical at a convenient rate (t/sub 1/2/approx. =1 h) to be followed by ESR at 77 K in the deuterated compound. The reaction can also be induced by light with lambda<700 nm. Reaction mechanisms and the isotope effect are discussed.

• Research Organization: The Studsvik Science Research Laboratory, S-611 82 Nykoeping, Sweden
• OSTI ID: 6903909
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 73:10; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ABSORPTION SPECTRA
ACTIVATION ENERGY
ALKYL RADICALS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DECOMPOSITION
DEUTERATION
DEUTERIUM
ELECTRON SPIN RESONANCE
ELECTRONS
ELEMENTARY PARTICLES
ENERGY
FERMIONS
HYDROGEN ISOTOPES
ISOTOPE EFFECTS
ISOTOPES
LEPTONS
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
RESONANCE
SPECTRA
STABLE ISOTOPES
TRAPPED ELECTRONS