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• W2083713427 endingPage "610" @default.
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• W2083713427 abstract "Electron spin-lattice relaxation times (T1e) for the major radicals in γ-irradiated polycrystalline samples of glycylglycine, l-alanine, 2,4,6-tri-tert-butyl-phenol, and 4-methyl-2,6-di-tert-butyl-phenol were measured as a function of temperature using pulsed EPR. CW-saturation recovery (CW-SR) were obtained at X-band (9.1 GHz) and S-band (3.0 GHz) between about 10 and 295 K. Inversion recovery, echo-detected saturation recovery (ED-SR), and pulsed electron−electron double resonance (ELDOR) curves were obtained at X-band between 77 and about 295 K. For 2,4,6-tri-tert-butyl-phenoxy radical, which has a single-line EPR spectrum, the recovery times obtained by the three methods were in good agreement and were assigned as T1e. For the three radicals with resolved hyperfine splitting, spectral diffusion caused the recovery times observed by inversion recovery or ED-SR to be significantly shorter than T1e obtained by CW-SR or ELDOR. Spectral diffusion processes were observed directly by pulsed ELDOR experiments, and time constants for cross relaxation and nuclear relaxation were obtained by modeling the ELDOR curves. For irradiated l-alanine and for the 4-methyl-2,6-tert-butyl-phenoxy radical at some temperatures, the effects of rapid cross relaxation on CW-SR curves could not be fully mitigated even by long saturating pulses, and T1e could only be determined by ELDOR. For the radicals in γ-irradiated l-alanine, 2,4,6-tri-tert-butyl-phenol, and 4-methyl-2,6-di-tert-butyl-phenol, methyl group rotation makes significant contributions to T1e at temperatures where the rate of rotation of a methyl group is comparable to the microwave frequency. Activation energies for methyl rotation were determined by modeling the temperature dependence of T1e at X-band and S-band. In temperature ranges where methyl rotation did not dominate, T1e was dominated by Raman, direct, or local mode processes." @default.
• W2083713427 created "2016-06-24" @default.
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• W2083713427 date "2003-01-10" @default.
• W2083713427 modified "2023-09-27" @default.
• W2083713427 title "Electron Spin-Lattice Relaxation Processes of Radicals in Irradiated Crystalline Organic Compounds" @default.
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• W2083713427 doi "https://doi.org/10.1021/jp021504h" @default.
• W2083713427 hasPublicationYear "2003" @default.
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