Electron Spin Resonance Spectrum of XeF in γ-Irradiated Xenon Tetrafluoride

Abstract
The radical XeF has been detected by means of electron spin resonance in a single crystal of XeF4 γ‐irradiated at 77°K. The following hyperfine interaction constants were obtained for magnetic field directions parallel and perpendicular to the Xe–F bond: F19=2649 Mc, F19=540 Mc, Xe129=2368 Mc, and Xe129=1224 Mc. The unpaired electron occupies a σ orbital, and it was shown from parameters derived from the respective atomic wavefunctions that the orbital is predominantly F 2p and Xe 5p in character. The experimentally determined g values for XeF were g=1.9740, g=2.1251. Departures from the free‐spin value are interpreted in terms of interaction between the orbital ground state and excited states of the molecule.

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