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Core level electron binding energies of realgar (As₄S₄)

¹ Mining and Mineral Sciences Laboratory, CANMET, Natural Resources Canada, 555 Booth Street, Ottawa, Ontario K1A 0G1, Canada
² The Department of Earth Sciences, University of Western Ontario, London, Ontario N6A 5B7, Canada

Correspondence: ^* E-mail: apratt{at}nrcan.gc.ca

XPS broad scans and high-resolution narrow-region spectra were collected from fresh realgar (As₄S₄) surfaces to measure core level S and As binding energies. Reasonably accurate As and S concentrations were determined from XPS broad scans using peak areas and manufacturer supplied sensitivity factors. High resolution S(2p) and As(3d) narrow region spectra were comprised of photoelectron emissions indicative of As and S in intermediate oxidation states akin to binding energies of As and S polymeric species. S(2p) spectra were interpreted using only S contributions expected from the bulk mineral matrix and showed that S was not greatly affected by surface state phenomena. This was attributed to breakage of intermolecular van der Waals bonds rather than covalent interatomic bonds. As(3d) spectra were found to contain two contributions one from As atoms in As₄S₄ molecules in the bulk mineral matrix and another possibly from As atoms in molecules situated at the surface.