The far-uv photolysis of phosphine sorbed in cancrinite matrix at 77 K has been studied by epr spectroscopy. Cancrinite is demonstrated to stabilise the photolytically generated radicals ·PH2, ·P and ·H. Computer simulation of the entire lineshapes has been employed to assess the spin Hamiltonian parameters for both ·PH2 and ·P. The intensity distribution pattern of the ·PH2 spectrum at 77 K is indicative of a thermally-equilibrated population of rotational states of this radical in its matrix environment. The similarity of the epr data of ·PH2 trapped in cancrinite to that isolated in rare gas matrices, as well as theisotropic nature of the31P and1H hyperfine couplings in the former situation, suggest that ·PH2 is trapped in pseudospherical cavities of cancrinite with minimal matrix perturbations. Marked departures are observed for theg- andA- values of cancrinite-trapped P atoms as compared with the gasphase counterparts.
Volume 134, 2022
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