CORRELATIONS BETWEEN PHOTOINDUCED EPR AND PHOTOCONDUCTIVITY INTONE-THF SOLUTION CHARGE-TRANSFER COMPLEX

Journal Article · Tue Dec 08 04:00:00 EST 1964 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.1695812· OSTI ID:920070

Ilten, David F.; Calvin, Melvin

Reversible photoinduced electron paramagnetic resonance (EPR) signals and photoconductivity were observed when a solution of tetracyancethylene (TCNE) in tetrahydrofuran (THF) was irradiated in the charge-transfer band of the complex formed between these two compounds. The eleven-line hyperfine structure of the EPR spectrum which was obtained demonstrated the presence of TCNE negative ion radical. The concentration of this radical was found to be directly proportional to the square root of the light intensity. Second order decay kinetics were followed when the light was shut off. Both the EPR signal and the photoconductivity rose initially as the square of the time. The latter portions of the growth curves could be fit to the latter portions of a hyperbolic tangential growth curve. From these data a reaction mechanism was proposed. The rate law dn/dt + kn{sup 2} = {alpha}L(1-e{sup -{beta}t}) = 0, where n = the concentration of radicals, t = the time, k, {alpha}, and {beta} are rate constants, and L = the light intensity, described both the photo-induced EPR and the photoconductivity within the limits of experimental accuracy.

• Research Organization: Ernest Orlando Lawrence Berkeley NationalLaboratory, Berkeley, CA (US)
• Sponsoring Organization: USAEC
• DOE Contract Number: AC02-05CH11231
• OSTI ID: 920070
• Report Number(s): UCRL--11374-Rev.
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 11 Vol. 42; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CHEMICAL REACTION KINETICS
ELECTRON SPIN RESONANCE
IRRADIATION
ORGANIC NITROGEN COMPOUNDS
PHOTOCONDUCTIVITY