title: Raman spectroscopic study of the hydroxy-phosphate mineral plumbogummite PbAl₃(PO₄)₂(OH,H₂O)₆.
abstract: Plumbogummite PbAl(3)(PO(4))(2)(OH,H(2)O)(6) is a mineral of environmental significance and is a member of the alunite-jarosite supergroup. The molecular structure of the mineral has been investigated by Raman spectroscopy. The spectra of different plumbogummite specimens differ although there are many common features. The Raman spectra prove the spectral profile consisting of overlapping bands and shoulders. Raman bands and shoulders observed at 971, 980, 1002 and 1023 cm(-1) (China sample) and 913, 981, 996 and 1026 cm(-1) (Czech sample) are assigned to the ν(1) symmetric stretching modes of the (PO(4))(3-), at 1002 and 1023 cm(-1) (China) and 996 and 1026 cm(-1) to the ν(1) symmetric stretching vibrations of the (O(3)POH)(2-) units, and those at 1057, 1106 and 1182 (China) and at 1102, 1104 and 1179 cm(-1) (Czech) to the ν(3) (PO(4))(3-) and ν(3) (PO(3)) antisymmetric stretching vibrations. Raman bands and shoulders at 634, 613 and 579 cm(-1) (China) and 611 and 596 cm(-1) (Czech) are attributed to the ν(4) (δ) (PO(4))(3-) bending vibrations and those at 507, 494 and 464 cm(-1) (China) and 505 and 464 cm(-1) (Czech) to the ν(2) (δ) (PO(4))(3-) bending vibrations. The Raman spectrum of the OH stretching region is complex. Raman bands and shoulders are identified at 2824, 3121, 3249, 3372, 3479 and 3602 cm(-1) for plumbogummite from China, and at 3077, 3227, 3362, 3480, 3518 and 3601 cm(-1) for the Czech Republic sample. These bands are assigned to the ν OH stretching modes of water molecules and hydrogen ions. Approximate O-H⋯O hydrogen bond lengths inferred from the Raman spectra vary in the range >3.2-2.62Å (China) and >3.2-2.67Å (Czech). The minority presence of some carbonate ions in the plumbogummite (China sample) is connected with distinctive intensity increasing of the Raman band at 1106 cm(-1), in which may participate the ν(1) (CO(3))(2-) symmetric stretching vibration overlapped with phosphate stretching vibrations.
authors.affiliation: School of Chemistry, Physics and Mechanical Engineering, Science and Engineering, Faculty Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia. r.frost@qut.edu.au
authors.forename: Ray L
authors.initials: RL
authors.lastname: Frost
authors.forename: Sara J
authors.initials: SJ
authors.lastname: Palmer
authors.forename: Yunfei
authors.initials: Y
authors.lastname: Xi
authors.forename: Jiří
authors.initials: J
authors.lastname: Čejka
authors.forename: Jiří
authors.initials: J
authors.lastname: Sejkora
authors.forename: Jakub
authors.initials: J
authors.lastname: Plášil
mesh_terms: D000535:Aluminum / Q000737:chemistry; D017607:Aluminum Compounds / Q000737:chemistry; D005290:Ferric Compounds / Q000737:chemistry; D007854:Lead / Q000737:chemistry*; D008903:Minerals / Q000737:chemistry*; D010710:Phosphates / Q000737:chemistry*; D017680:Potassium Compounds / Q000737:chemistry; D013059:Spectrum Analysis, Raman; D013431:Sulfates / Q000737:chemistry
chemical_list: D017607:Aluminum Compounds; D005290:Ferric Compounds; D008903:Minerals; D010710:Phosphates; D017680:Potassium Compounds; D013431:Sulfates; C473131:alunite; C492331:jarosite; D007854:Lead; D000535:Aluminum