Electron–electron double resonance study of coherent and random rotational motion of methyl groups
- 15 November 1975
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 63 (10), 4405-4411
- https://doi.org/10.1063/1.431158
Abstract
Electron–electron double resonance(ELDOR) spectra are reported for the free radical CH3C̊ (COOH)2 in x‐irradiated crystals of methylmalonic acid over the temperature range 10–50 K. At low temperatures tunneling sidebands are observed corresponding to simultaneous flips of the electron spin and changes in the tunneling rotation state of the methyl group. The previous assignment of weak satellite lines of the electron spin resonance(ESR) spectrum to these transitions is unequivocally confirmed, and sidebands obscured in the ESR spectrum are clearly observed in the ELDOR spectrum with the expected frequencies and intensities. The temperature dependence of the frequencies confirms the previous observation of the temperature dependence of the frequency of tunneling rotation of the methyl group. A sequence of changes with rising temperature in the relative amplitudes of lines in the ELDOR spectra is accounted for in a qualitative way as a consequence of the changing rates of several cross relaxation processes, all of which arise as a consequence of the modulation of the electron–proton hyperfine interaction by thermally activated rotation of the methyl group about its symmetry axis.Keywords
This publication has 9 references indexed in Scilit:
- Paramagnetic RelaxationAnnual Review of Physical Chemistry, 1974
- A model for a temperature-dependent frequency distribution of methyl group tunnelling splittingsJournal of Physics C: Solid State Physics, 1974
- Temperature dependence of methyl group tunnelling rotation frequencyJournal of Physics C: Solid State Physics, 1974
- Electron-electron double resonance of irradiated dimethylmalonic acid, α-aminoisobutyric acid, and L-alanine single crystals: The role of methyl substituentsThe Journal of Chemical Physics, 1973
- Tunnelling sidebands of methyl group hyperfine structureJournal of Physics C: Solid State Physics, 1972
- Methyl group tunnelling rotation frequency in γ-irradiated methyl malonic acid crystalsJournal of Physics C: Solid State Physics, 1972
- Quantum Effects of Methyl-Group Rotations in Magnetic Resonance: ESR Splittings and LinewidthsThe Journal of Chemical Physics, 1965
- Electron Spin Resonance of Irradiated Single Crystals of Alanines: Hindered Rotation of the Methyl Group in a Free RadicalThe Journal of Chemical Physics, 1962
- Electron Spin Resonance and Internal Rotation of the Methyl Group in the CH3Ċ(COOH)2 RadicalThe Journal of Chemical Physics, 1962