Molecular manganese sulfide clusters formed by laser ablation

Laser ablation of solid MnS yields in the gas phase polysulfane cations [MnSn](+) (4 less than or equal to n less than or equal to 11), and anionic clusters [MnxSx](-) and [MnxSx+1](-) (2 less than or equal to x less than or equal to 22), together with clusters [MnxSxO](-) (4 less than or equal to x less than or equal to 22) formed from adventitious water. These ions were detected and investigated further by Fourier-transform ion cyclotron resonance mass spectrometry. There are no major discontinuities in abundance or especially stable structures in the series [MnxSx](-) and [MnxSx+1](-). There are some differences in the distributions of ions formed by the pink and green forms of solid MnS, with the pink form generating more sulfur vapour and polysulfane cations, and the green form more suitable for the formation of cluster anions. The cations [MnSn](+) lose S-2 on collisional activation. The cluster anions [MnxSy](-) are generally unreactive and not oxidised by N2O, but on reaction with H2S (g) they undergo protonation or add one or two S atoms to form also the new products [MnxSx+2](-) (4 less than or equal to x less than or equal to 8). The compositions [MnxSx](-) and [MnxSx+1](-) represent a well defined region of stability for anions, and for the neutral clusters from which they are believed to be formed by electron attachment.