The anomalous extinction of specific Kikuchi bands has been recently o
bserved in the X-ray photoelectron diffraction (XPED) pattern for F1s
emission from a CaF2(111) surface; even though the corresponding struc
ture factors are not zero. To explain this phenomenon, we have derived
a novel extinction rule and have shown that the extinction of Kikuchi
bands in XPED depends not only on the structure factors but also on t
he lattice sites of source atoms. This rule can be used to locate the
lattice sites of impurities in single-crystal substrates.