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Unambiguous observation of F-atom core-hole localization in CF4 through body-frame photoelectron angular distributions
AuthorMcCurdy, C. W.
Rescigno, T. N.
Trevisan, C. S.
Lucchese, R. R.
Schoeffler, M. S.
Stammer, P. M.
Landers, A. L.
Williams, J. B.
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A dramatic symmetry breaking in K-shell photoionization of the CF4 molecule in which a core-hole vacancy is created in one of four equivalent fluorine atoms is displayed in the molecular frame angular distribution of the photoelectrons. Observing the photoejected electron in coincidence with an F+ atomic ion after Auger decay is shown to select the dissociation path where the core hole was localized almost exclusively on that atom. A combination of measurements and ab initio calculations of the photoelectron angular distribution in the frame of the recoiling CF3+ and F+ atoms elucidates the underlying physics that derives from the Ne-like valence structure of the F(1s(-1)) core-excited atom.