The vertical I.P.'s of the first eight ionizations in the XeF2molecule have been determined, and they compare favorably with the results of Gaussianhyphen;type orbital calculations. The first two ionic states of XeF2are the2Pgr;3/2(12.42 eV) and2Pgr;1/2(12.89 eV) spinndash;orbit components formed by ionization from the highesthyphen;filledpgr;orbitallpar;5pgr;urpar;. As judged by the vibronic structure of the transitions, the two upper states are linear, with Xesngbnd;F distances very much like those of the ground state. The fifth (15.60 eV) and sixth (16.00 eV) I.P.'s similarly involve the ejection of an electron from the4pgr;uorbitals, and thus they are separated by the action of spinndash;orbit coupling. Substitution of Heiiagr;excitation (40.82 eV) for the Heiagr;excitation (21.21 eV) results in both the additional ionization of electrons from the9sgr;gmolecular orbital (22.5 eV), and a drastic change in the relative intensities of certain peaks in the lower I.P. region. Rydberg bands in the optical spectrum of XeF2can be correlated with those of the photoelectron spectrum, yielding assignments in essential agreement with those given by earlier workers. The work with the Heiiresonance line is described in some detail because a description of its use in photoelectron spectroscopy has not previously appeared in the literature.
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