Chromium/phosphorus binary cluster ions, [Cr n P m ] AE , produced by laser (532nm) ablation on a tablet of well-mixed chromium and red phosphorus powder, were studied with a home-built tandem time-of-flight (TOF) mass spectrometer. The clusters thus formed are mostly rich in phosphorus. There is an odd-even oscillation in the intensity of the [CrP m ] series, i.e. the mass peaks of even m are higher than those of odd m. The peaks of [CrP 4 ] and [CrP 8 ] are especially prominent, which may be ascribed to the specific stability of P 4 sub-structures. There are also some intense peaks in the spectrum assigned to [Cr 3 P 8 ] , [Cr 4 P 9 ] , [Cr 5 P 11 ] , [Cr 6 P 12 ] , [Cr 8 P 14 ] clusters, etc., which have stable compositions. The stability of these species is consistent with a simple qualitative electronic structure model, in which the valence electrons of P are filled into the d orbitals of Cr. The photodissociation of some cluster ions was also studied. DFT calculations were performed on three small cluster ions to provide some insight into their structures.
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