NDLI: Librational dynamics of nitroxide molecules in a molecular glass studied by echo-detected EPR

Content Provider	Springer Nature Link
Author	Kirilina, E. P. Dzuba, S. A. Maryasov, A. G. Tsvetkov, Yu. D.
Copyright Year	2001
Abstract	Nitroxides 2,2,6,6-tetramethyl-4-piperidone N-oxide (tempone), 3-carboxy-proxyl and potassium peroxylamine disulfonate (Fremy salt) in glycerol solution were studied in a wide temperature range near the glass transition temperatureT g. The echo-detected (ED) electron paramagnetic resonance (EPR) lineshape reveals strong dependence on the time interval τ between the echo-forming microwave pulses which is readily explained by anisotropic phase relaxation. Employing a librational model of molecular motion and the Redfield relaxation theory, spectra were simulated for the τ’s varying in a large interval. The anisotropic relaxation rate increases with temperature increase and it is larger for nitroxide with a larger molecular size. The mean-squared amplitude of motion, obtained from reduced hyperfine splitting in continuous-wave EPR, near Tg linearly depends on temperature which is characteristic of harmonic solids. For tempone in a host crystal 2,2,4,4-tetramethyl-cyclobutan-1, 3-dione the anisotropic spin relaxation rate decreases with temperature increase so the found feature solely belongs to a glassy state. A new approach is proposed for modeling slow wobbling motion in a restricted angular space.
Starting Page	203
Ending Page	221
Page Count	19
File Format	PDF
ISSN	09379347
Journal	Applied Magnetic Resonance
Volume Number	21
Issue Number	2
e-ISSN	16137507
Language	English
Publisher	Springer-Verlag
Publisher Date	2001-01-01
Publisher Place	Vienna
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Solid State Physics Spectroscopy/Spectrometry Physical Chemistry Organic Chemistry
Content Type	Text
Resource Type	Article
Subject	Atomic and Molecular Physics, and Optics

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