Raman spectroscopic study of the arsenite minerals leiteite ZnAs2O4 , reinerite Zn3(AsO3)2 and cafarsite Ca5(Ti,Fe,Mn)7(AsO3)12.4H2O

The selected arsenite minerals leiteite, reinerite and cafarsite have been studied by Raman spectroscopy. DFT calculations enabled the position of AsO22- symmetric stretching mode at 839 cm-1, the antisymmetric stretching mode at 813 cm-1, and the deformation mode at 449 cm-1 to be calculated. The Raman spectrum of leiteite shows bands at 804 and 763 cm-1 assigned to the As2O42- symmetric and antisymmetric stretching modes. The most intense Raman band of leiteite is the band at 457 cm-1 and is assigned to the ν2 As2O42- bending mode. A comparison of the Raman spectrum of leiteite is made with the arsenite minerals reinerite and cafarsite.

Molecular structure of Mg-Al, Mn-Al and Zn-Al halotrichites : an infrared spectroscopic study

Near infrared (NIR), X-ray diffraction (XRD) and infrared (IR) spectroscopy have been applied to halotrichites of the formula MgAl2(SO4)4∙22H2O, MnAl2(SO4)4∙22H2O and ZnAl2(SO4)4∙22H2O. Comparison of the halotrichites in different spectral regions has shown that the incorporation of a divalent transition metal into the halotrichite structure causes a shift in OH stretching band positions to lower wavenumbers. Therefore, an increase in hydrogen bonded water is observed for divalent cations with a larger molecular mass. XRD has confirmed the formation of halotrichite for all three samples and characteristic peaks of halotrichite have been identified at 18.5 and 24.5° 2θ, along with a group of six peaks between 5 and 15° 2θ. It has been observed that Mg-Al and Mn-Al halotrichite are very similar in structure, while Zn-Al showed several differences particularly in the NIR spectra. This work has shown that halotrichite structures can be synthesised and characterised by infrared and NIR spectroscopy.

Vibrational spectroscopic characterization of the phosphate mineral ludlamite (Fe,Mn,Mg)3(PO4)2⋅4H2O – a mineral found in lithium bearing pegmatites

The objective of this work is to analyze ludlamite (Fe,Mn,Mg)3(PO4)2⋅4H2O from Boa Vista mine, Galiléia, Brazil and to assess the molecular structure of the mineral. The phosphate mineral ludlamite has been characterized by EMP-WDS, Raman and infrared spectroscopic measurements. The mineral is shown to be a ferrous phosphate with some minor substitution of Mg and Mn. Raman bands at 917 and 950 cm−1 are assigned to the symmetric stretching mode of and units. Raman bands at 548, 564, 599 and 634 cm−1 are assigned to the ν4 bending modes. Raman bands at 2605, 2730, 2896 and 3190 cm−1 and infrared bands at 2623, 2838, 3136 and 3185 cm−1 are attributed to water stretching vibrations. By using a Libowitzky empirical function, hydrogen bond distances are calculated from the OH stretching wavenumbers. Strong hydrogen bonds in the structure of ludlamite are observed as determined by their hydrogen bond distances. The application of infrared and Raman spectroscopy to the study of ludlamite enables the molecular structure of the pegmatite mineral ludlamite to be assessed.

Vibrational spectroscopic characterization of the phosphate mineral hureaulite – (Mn, Fe)5(PO4)2(HPO4)2·4(H2O)

This research was done on hureaulite samples from the Cigana claim, a lithium bearing pegmatite with triphylite and spodumene. The mine is located in Conselheiro Pena, east of Minas Gerais. Chemical analysis was carried out by Electron Microprobe analysis and indicated a manganese rich phase with partial substitution of iron. The calculated chemical formula of the studied sample is: (Mn3.23, Fe1.04, Ca0.19, Mg0.13)(PO4)2.7(HPO4)2.6(OH)4.78. The Raman spectrum of hureaulite is dominated by an intense sharp band at 959 cm−1 assigned to PO stretching vibrations of HPO42− units. The Raman band at 989 cm−1 is assigned to the PO43− stretching vibration. Raman bands at 1007, 1024, 1047, and 1083 cm−1 are attributed to both the HOP and PO antisymmetric stretching vibrations of HPO42− and PO43− units. A set of Raman bands at 531, 543, 564 and 582 cm−1 are assigned to the ν4 bending modes of the HPO42− and PO43− units. Raman bands observed at 414, and 455 cm−1 are attributed to the ν2 HPO42− and PO43− units. The intense A series of Raman and infrared bands in the OH stretching region are assigned to water stretching vibrations. Based upon the position of these bands hydrogen bond distances are calculated. Hydrogen bond distances are short indicating very strong hydrogen bonding in the hureaulite structure. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral hureaulite to be understood.

Vibrational spectroscopic characterization of the phosphate mineral series eosphorite–childrenite–(Mn,Fe)Al(PO4)(OH)2·(H2O)

The phosphate mineral series eosphorite–childrenite–(Mn,Fe)Al(PO4)(OH)2·(H2O) has been studied using a combination of electron probe analysis and vibrational spectroscopy. Eosphorite is the manganese rich mineral with lower iron content in comparison with the childrenite which has higher iron and lower manganese content. The determined formulae of the two studied minerals are: (Mn0.72,Fe0.13,Ca0.01)(Al)1.04(PO4, OHPO3)1.07(OH1.89,F0.02)·0.94(H2O) for SAA-090 and (Fe0.49,Mn0.35,Mg0.06,Ca0.04)(Al)1.03(PO4, OHPO3)1.05(OH)1.90·0.95(H2O) for SAA-072. Raman spectroscopy enabled the observation of bands at 970 cm−1 and 1011 cm−1 assigned to monohydrogen phosphate, phosphate and dihydrogen phosphate units. Differences are observed in the area of the peaks between the two eosphorite minerals. Raman bands at 562 cm−1, 595 cm−1, and 608 cm−1 are assigned to the �4 bending modes of the PO4, HPO4 and H2PO4 units; Raman bands at 405 cm−1, 427 cm−1 and 466 cm−1 are attributed to the �2 modes of these units. Raman bands of the hydroxyl and water stretching modes are observed. Vibrational spectroscopy enabled details of the molecular structure of the eosphorite mineral series to be determined.

Metal hexaborides with Sc, Ti or Mn

Comparison of well-determined single crystal data for stoichiometric, or near-stoichiometric, metal hexaborides con-firm previously identified lattice parameter trends using powder diffraction. Trends for both divalent and trivalent forms suggest that potential new forms for synthesis include Sc and Mn hexaborides. Density Functional Theory (DFT) calculations for KB6, CaB6, YB6, LaB6, boron octahedral clusters and Sc and Mn forms, show that the shapes of bonding orbitals are defined by the boron framework. Inclusion of metal into the boron framework induces a reduction in energy ranging from 1 eV to 6 eV increasing with ionic charge. For metals with d1 character, such a shift in energy brings a doubly degenerate band section along the G-M reciprocal space direction within the conduction bands tangential to the Fermi surface. ScB6 band structure and density of states calculations show directional and gap characteristics similar to those of YB6 and LaB6. These calculations for ScB6 suggest it may be possible to realize superconductivity in this compound if synthesized.

Electrochemically-induced TCNQ/Mn TCNQ 2 (H2O) 2 (TCNQ= 7, 7, 8, 8-Tetracyanoquinodimethane) solid-solid interconversion : two voltammetrically distinct processes that allow selective generation of nanofiber or nanorod network morphologies

Unlike the case with other divalent transition metal M\[TCNQ](2)(H(2)O)(2) (M = Fe, Co, Ni) analogues, the electrochemically induced solid-solid phase interconversion of TCNQ microcrystals (TCNQ = 7,7,8,8-tetracyanoquinodimethane) to Mn\[TCNQ](2)(H(2)O)(2) occurs via two voltammetrically distinct, time dependent processes that generate the coordination polymer in nanofiber or rod-like morphologies. Careful manipulation of the voltammetric scan rate, electrolysis time, Mn(2+)((aq)) concentration, and the method of electrode modification with solid TCNQ allows selective generation of either morphology. Detailed ex situ spectroscopic (IR, Raman), scanning electron microscopy (SEM), and X-ray powder diffraction (XRD) characterization clearly establish that differences in the electrochemically synthesized Mn-TCNQ material are confined to morphology. Generation of the nanofiber form is proposed to take place rapidly via formation and reduction of a Mn-stabilized anionic dimer intermediate, \[(Mn(2+))(TCNQ-TCNQ)(2)(*-)], formed as a result of radical-substrate coupling between TCNQ(*-) and neutral TCNQ, accompanied by ingress of Mn(2+) ions from the aqueous solution at the triple phase TCNQ/electrode/electrolyte boundary. In contrast, formation of the nanorod form is much slower and is postulated to arise from disproportionation of the \[(Mn(2+))(TCNQ-TCNQ)(*-)(2)] intermediate. Thus, identification of the time dependent pathways via the solid-solid state electrochemical approach allows the crystal size of the Mn\[TCNQ](2)(H(2)O)(2) material to be tuned and provides new mechanistic insights into the formation of different morphologies.

A vibrational spectroscopic study of the silicate mineral inesite Ca2(Mn,Fe)₇Si10O28(OH)⋅5H2O

We have studied the hydrated hydroxyl silicate mineral inesite of formula Ca2(Mn,Fe)7Si10O28(OH)⋅5H2O using a combination of scanning electron microscopy with EDX and Raman and infrared spectroscopy. SEM analysis shows the mineral to be a pure monomineral with no impurities. Semiquantitative analysis shows a homogeneous phase, composed by Ca, Mn2+, Si and P, with minor amounts of Mg and Fe. Raman spectrum shows well resolved component bands at 997, 1031, 1051, and 1067 cm-1 attributed to a range of SiO symmetric stretching vibrations of [Si10O28] units. Infrared bands found at 896, 928, 959 and 985 cm-1 are attributed to the OSiO antisymmetric stretching vibrations. An intense broad band at 653 cm-1 with shoulder bands at 608, 631 and 684 cm-1 are associated with the bending modes of the OSiO units of the 6- and 8-membered rings of the [Si10O28] units. The sharp band at 3642 cm-1 with shoulder bands at 3612 and 3662 cm-1 are assigned to the OH stretching vibrations of the hydroxyl units. The broad Raman band at 3420 cm-1 with shoulder bands at 3362 and 3496 cm-1 are assigned to the water stretching vibrations. The application of vibrational spectroscopy has enabled an assessment of the molecular structure of inesite to be undertaken.