Rotation of methyl radicals in a solid argon matrix

Electron spin resonance (ESR) measurements were carried out to study the rotation of methyl radicals (CH3) in a solid argon matrix at 14-35 K temperatures. The radicals were produced by dissociating methane by plasma bursts generated either by a focused 193 nm laser radiation or a radio frequency discharge device during the gas condensation on the substrate. The ESR spectrum exhibits axial symmetry at the lowest temperature and is ascribed to ground state molecules with symmetric total nuclear spin function I=3/2. The hyperfine anisotropy (Aparallel)-Aperpendicular) was found to be -0.01 mT, whereas that of the g value was 2.5x10(-5). The anisotropy is observed for the first time in Ar and is manifested by the splitting of the low-field transition. Elevation of temperature leads reversibly to the appearance of excited state contribution having antisymmetric I=1/2. As a function of the sample temperature, the relative intensities of symmetric and antisymmetric spin states corresponding to ground and excited rotor states, respectively, proton hyperfine and electron g-tensor components, and spin-lattice relaxation rates were determined by a numerical fitting procedure. The experimental observations were interpreted in terms of a free rotation about the C3 axis and a thermal activation of the C2-type rotations above 15 K. The ground and excited rotational state energy levels were found to be separated by 11.2 cm-1 and to exhibit significantly different spin-lattice coupling. A crystal field model has been applied to evaluate the energy levels of the hindered rotor in the matrix, and crystal field parameter varepsilon4=-200 cm-1, corresponding to a 60 cm-1 effective potential barrier for rotation of the C3 axis, was obtained.