title: Theoretical and experimental study of the vibrational spectra of sarkinite Mn2(AsO4)(OH) and adamite Zn2(AsO4)(OH).
abstract: The arsenate hydroxyl-bearing minerals sarkinite and adamite were studied with vibrational spectroscopic (IR and Raman) and quantum theoretical methods. The observed IR bands in the higher (1100-600 cm(-1)) and especially lower (600-450 cm(-1)) frequency region of AsO4 vibrations could clearly discriminate between the studied analogues. The differences between their crystal structures are much pronounced in both IR and Raman OH-stretching regions. Namely, a single strong band is found in the case of orthorhombic adamite compared to four weaker bands observed in corresponding IR and Raman spectral regions of monoclinic sarkinite. Essentially all bands in the experimental spectra, collected at both room and liquid nitrogen temperature, were tentatively assigned. To support the tentative assignment of bands in the vibrational spectra of the mentioned minerals, periodic pseudopotential plane wave density functional theory calculations were carried out. Geometry optimizations of the 3D periodic systems included both optimizations of the atomic positions within the unit cell and of the unit cell itself. In most cases, the assignments were either supported or implied by the obtained theoretical data. It is worth mentioning that this is the first experimental and theoretical study of the vibrational spectra of the very-rare sarkinite mineral.
authors.affiliation: Institute of Chemistry, Faculty of Natural Sciences and Mathematics, SS. Cyril and Methodius University, Arhimedova 5, 1000 Skopje, Macedonia. petremak@pmf.ukim.mk
authors.forename: Petre
authors.initials: P
authors.lastname: Makreski
authors.forename: Stefan
authors.initials: S
authors.lastname: Jovanovski
authors.forename: Ljupco
authors.initials: L
authors.lastname: Pejov
authors.forename: Gert
authors.initials: G
authors.lastname: Kloess
authors.forename: Hans-Joachim
authors.initials: HJ
authors.lastname: Hoebler
authors.forename: Gligor
authors.initials: G
authors.lastname: Jovanovski
mesh_terms: D001149:Arsenates / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry; D008345:Manganese / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D013696:Temperature; D014732:Vibration
chemical_list: D001149:Arsenates; C585854:adamite; C585853:sarkinite; D017665:Hydroxyl Radical; D008345:Manganese
keywords: Adamite; Infrared and Raman spectra; Pseudopotential plane wave density functional theory approach; Sarkinite; Theoretical spectra