Electron spin resonance of chlorine dioxide in inert matrices at 4.2°K

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Abstract
The electron paramagnetic resonance spectrum of ClO2 trapped in neon, argon, and krypton matrices has been investigated at 4.2°K. The linewidths of the polycrystalline spectra were narrow enough so that forbidden transitions due to the nuclear Zeeman and nuclear quadrupole interactions could be resolved. The g, A, and Q tensors for each matrix were determined by comparison between experimental and computer simulated spectra. Partial orientation has been observed in all three matrices; the preferred orientation is with the molecular plane parallel to the deposition surface. Upon rotating the magnetic field to a position where it is either parallel or perpendicular to the deposition plane, marked differences in line intensities were apparent and an estimate of an orientation distribution function was made from comparison with simulated spectra. Annealing the argon matrix led to the appearance of a second trapping site with slightly different hyperfine and g tensors. This site is thought to be a substitutional one. The shifts of the hyperfine and g tensors in the three matrices have been qualitatively discussed in terms of van der Waals and Pauli interaction forces.