A Raman spectroscopic study of the antimony mineral klebelsbergite Sb4O4(OH)2(SO4)

Many minerals based upon antimonite and antimonate anions remain to be studied. Most of the bands occur in the low wavenumber region, making the use of infrared spectroscopy difficult. This problem can be overcome by using Raman spectroscopy. The Raman spectra of the mineral klebelsbergite Sb₄O₄(OH)₂(SO₄) were studied and related to the structure of the mineral. The Raman band observed at 971 cm⁻¹ and a series of overlapping bands are observed at 1029, 1074, 1089, 1139 and 1142 cm⁻¹ are assigned to the SO₄²⁻ν₁ symmetric and ν₃ antisymmetric stretching modes, respectively. Two Raman bands are observed at 662 and 723 cm⁻¹, which are assigned to the Sb O ν₃ antisymmetric and ν₁ symmetric stretching modes, respectively. The intense Raman bands at 581, 604 and 611 cm⁻¹ are assigned to the ν₄ SO₄²⁻ bending modes. Two overlapping bands at 481 and 489 cm⁻¹ are assigned to the ν₂ SO₄²⁻ bending mode. Low‐intensity bands at 410, 435 and 446 cm⁻¹ may be attributed to O Sb O bending modes. The Raman band at 3435 cm⁻¹ is attributed to the O H stretching vibration of the OH units. Multiple Raman bands for both SO₄²⁻ and Sb O stretching vibrations support the concept of the non‐equivalence of these units in the klebelsbergite structure. It is proposed that the two sulfate anions are distorted to different extents in the klebelsbergite structure. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the tellurite minerals: emmonsite Fe23+Te34+O9·2H2O and zemannite Mg0.5[Zn2+Fe3+(TeO3)3]4.5H2O

Raman spectroscopy has been used to study zemannite Mg_0.5[Zn²⁺Fe³⁺(TeO₃)₃]4.5H₂O and emmonsite Fe₂³⁺Te₃⁴⁺O₉·2H₂O. Raman bands for zemannite and emmonsite, observed at 740 and 650 cm⁻¹ and at 764 and 788 cm⁻¹, respectively, are attributed to the ν₁ (TeO₃)²⁻ symmetric stretching mode. The splitting of the symmetric stretching mode for emmonsite is in harmony with the results of X‐ray crystallography which shows three non‐equivalent TeO₃ units in the crystal structure. Two bands at 658 and 688 cm⁻¹ are assigned to ν₃ (TeO₃)²⁻ anti‐symmetric stretching modes. Raman bands observed at 372 and 408 cm⁻¹ for zemannite and 397 and 414 cm⁻¹ for emmonsite are attributed to the (TeO₃)²⁻ν₂(A₁) bending mode. The two Raman bands at 400 and 440 cm⁻¹ for emmonsite are ascribed to the ν₄(E) bending modes, while the band at 326 cm⁻¹ is due to the ν₂(A₁) bending vibration. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the tellurite minerals: graemite CuTeO3·H2O and teineite CuTeO3·2H2O

Tellurites may be subdivided according to formula and structure. There are five groups based upon the formulae (a) A(XO₃), (b) A(XO₃)·xH₂O, (c) A₂(XO₃)₃·xH₂O, (d) A₂(X₂O₅) and (e) A(X₃O₈). Raman spectroscopy has been used to study the tellurite minerals teineite and graemite; both contain water as an essential element of their stability. The tellurite ion should show a maximum of six bands. The free tellurite ion will have C_3v symmetry and four modes, 2A₁ and 2 E. Raman bands for teineite at 739 and 778 cm⁻¹ and for graemite at 768 and 793 cm⁻¹ are assigned to the ν₁ (TeO₃)²⁻ symmetric stretching mode while bands at 667 and 701 cm⁻¹ for teineite and 676 and 708 cm⁻¹ for graemite are attributed to the ν₃ (TeO₃)²⁻ antisymmetric stretching mode. The intense Raman band at 509 cm⁻¹ for both teineite and graemite is assigned to the water librational mode. Raman bands for teineite at 318 and 347 cm⁻¹ are assigned to the (TeO₃)²⁻ν₂(A₁) bending mode and the two bands for teineite at 384 and 458 cm⁻¹ may be assigned to the (TeO₃)²⁻ν₄(E) bending mode. Prominent Raman bands, observed at 2286, 2854, 3040 and 3495 cm⁻¹, are attributed to OH stretching vibrations. The values for these OH stretching vibrations provide hydrogen bond distances of 2.550(6) Å (2341 cm⁻¹), 2.610(3) Å (2796 cm⁻¹) and 2.623(2) Å (2870 cm⁻¹) which are comparatively short for secondary minerals. Copyright © 2008 John Wiley & Sons, Ltd.     

Natural halotrichites—an EDX and Raman spectroscopic study

Raman spectroscopy has been used to characterise four natural halotrichites: halotrichite FeSO₄.Al₂(SO₄)₃. 22H₂O, apjohnite MnSO₄.Al₂(SO₄)₃.22H₂O, pickingerite MgSO₄.Al₂(SO₄)₃.22H₂O and wupatkiite CoSO₄.Al₂(SO₄)₃.22H₂O. A comparison of the Raman spectra is made with the spectra of the equivalent synthetic pseudo‐alums. Energy dispersive X‐ray analysis (EDX) was used to determine the exact composition of the minerals. The Raman spectrum of apjohnite and halotrichite display intense symmetric bands at ∼985 cm⁻¹ assigned to the ν₁(SO₄)²⁻ symmetric stretching mode. For pickingerite and wupatkiite, an intense band at ∼995 cm⁻¹ is observed. A second band is observed for these minerals at 976 cm⁻¹ attributed to a water librational mode The series of bands for apjohnite at 1104, 1078 and 1054 cm⁻¹, for halotrichite at 1106, 1072 and 1049 cm⁻¹, for pickingerite at 1106, 1070 and 1049 cm⁻¹ and for wupatkiite at 1106, 1075 and 1049 cm⁻¹ are attributed to the ν₃(SO₄)²⁻ antisymmetric stretching modes of ν₃(B_g) SO₄. Raman bands at around 474, 460 and 423 cm⁻¹ are attributed to the ν₂(A_g) SO₄ mode. The band at 618 cm⁻¹ is assigned to the ν₄(B_g) SO₄ mode. The splitting of the ν₂, ν₃ and ν₄ modes is attributed to the reduction of symmetry of the SO₄ and it is proposed that the sulphate coordinates to water in the hydrated aluminium in bidentate chelation. Copyright © 2007 John Wiley & Sons, Ltd.     

Dussertite BaFe3+3(AsO4)2(OH)5—a Raman spectroscopic study of a hydroxy‐arsenate mineral

The mineral dussertite, a hydroxy‐arsenate mineral with formula BaFe³⁺₃(AsO₄)₂(OH)₅, has been studied by Raman spectroscopy complemented with infrared spectroscopy. The spectra of three minerals from different origins were investigated and proved to be quite similar, although some minor differences were observed. In the Raman spectra of the Czech dussertite, four bands are observed in the 800–950 cm⁻¹ region. The bands are assigned as follows: the band at 902 cm⁻¹ is assigned to the (AsO₄)³⁻ν₃ antisymmetric stretching mode, the one at 870 cm⁻¹ to the (AsO₄)³⁻ν₁ symmetric stretching mode, and those at 859 and 825 cm⁻¹ to the As‐OM^{2 + /3+} stretching modes and/or hydroxyl bending modes. Raman bands at 372 and 409 cm⁻¹ are attributed to the ν₂ (AsO₄)³⁻ bending mode and the two bands at 429 and 474 cm⁻¹ are assigned to the ν₄ (AsO₄)³⁻ bending mode. An intense band at 3446 cm⁻¹ in the infrared spectrum and a complex set of bands centred upon 3453 cm⁻¹ in the Raman spectrum are attributed to the stretching vibrations of the hydrogen‐bonded (OH)⁻ units and/or water units in the mineral structure. The broad infrared band at 3223 cm⁻¹ is assigned to the vibrations of hydrogen‐bonded water molecules. Raman spectroscopy identified Raman bands attributable to (AsO₄)³⁻ and (AsO₃OH)²⁻ units. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl mineral pseudojohannite Cu6.5[(UO2)4O4(SO4)2]2(OH)5·25H2O

Raman spectra of pseudojohannite were studied and related to the structure of the mineral. Observed bands were assigned to the stretching and bending vibrations of (UO₂)²⁺ and (SO₄)²⁻ units and of water molecules. The published formula of pseudojohannite is Cu_6.5(UO₂)₈[O₈](OH)₅[(SO₄)₄]·25H₂O. Raman bands at 805 and 810 cm⁻¹ are assigned to (UO₂)²⁺ stretching modes. The Raman bands at 1017 and 1100 cm⁻¹ are assigned to the (SO₄)²⁻ symmetric and antisymmetric stretching vibrations. The three Raman bands at 423, 465 and 496 cm⁻¹ are assigned to the (SO₄)²⁻ν₂ bending modes. The bands at 210 and 279 cm⁻¹ are assigned to the doubly degenerate ν₂ bending vibration of the (UO₂)²⁺ units. U O bond lengths in uranyl and O H···O hydrogen bond lengths were calculated from the Raman and infrared spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the hydroxy‐arsenate‐sulfate mineral chalcophyllite Cu18Al2(AsO4)4(SO4)3(OH)24·36H2O

The mixed anion mineral chalcophyllite Cu₁₈Al₂(AsO₄)₄(SO₄)₃(OH)₂₄·36H₂O has been studied by using Raman and infrared spectroscopies. Characteristic bands associated with arsenate, sulfate and hydroxyl units are identified. Broad bands in the OH stretching region are observed and are resolved into component bands. Estimates of hydrogen bond distances were made using a Libowitzky function. Both short and long hydrogen bonds were identified. Two intense bands at 841 and ∼814 cm⁻¹ are assigned to the ν₁ (AsO₄)³⁻ symmetric stretching and ν₃ (AsO₄)³⁻ antisymmetric stretching modes. The comparatively sharp band at 980 cm⁻¹ is assigned to the ν₁ (SO₄)²⁻ symmetric stretching mode, and a broad spectral profile centred upon 1100 cm⁻¹ is attributed to the ν₃ (SO₄)²⁻ antisymmetric stretching mode. A comparison of the Raman spectra is made with other arsenate‐bearing minerals such as carminite, clinotyrolite, kankite, tilasite and pharmacosiderite. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the mixed anion mineral yecoraite Bi5Fe3O9(Te4+O3)(Te6+O4)2·9H2O

Tellurates are rare minerals as the tellurate anion is readily reduced to the tellurite ion. Often minerals with both tellurate and tellurite anions are found. An example of such a mineral containing tellurate and tellurite is yecoraite. Raman spectroscopy has been used to study this mineral, the exact structure of which is unknown. Two Raman bands at 796 and 808 cm⁻¹ are assigned to the ν₁(TeO₄)²⁻ symmetric and ν₃(TeO₃)²⁻ antisymmetric stretching modes and Raman bands at 699 cm⁻¹ are attributed to the ν₃(TeO₄)²⁻ antisymmetric stretching mode and the band at 690 cm⁻¹ to the ν₁(TeO₃)²⁻ symmetric stretching mode. The intense band at 465 cm⁻¹ with a shoulder at 470 cm⁻¹ is assigned the (TeO₄)²⁻ and (TeO₃)²⁻ bending modes. Prominent Raman bands are observed at 2878, 2936, 3180 and 3400 cm⁻¹. The band at 3936 cm⁻¹ appears quite distinct and the observation of multiple bands indicates the water molecules in the yecoraite structure are not equivalent. The values for the OH stretching vibrations listed provide hydrogen bond distances of 2.625 Å (2878 cm⁻¹), 2.636 Å (2936 cm⁻¹), 2.697 Å (3180 cm⁻¹) and 2.798 Å (3400 cm⁻¹). This range of hydrogen bonding contributes to the stability of the mineral. A comparison of the Raman spectra of yecoraite with that of tellurate containing minerals kuranakhite, tlapallite and xocomecatlite is made. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the mineral finnemanite Pb5(As3+O3)3Cl

The arsenite mineral finnemanite Pb₅(As³⁺ O₃)₃Cl has been studied by Raman spectroscopy. The most intense Raman band at 871 cm⁻¹ is assigned to the ν₁(AsO₃)³⁻ symmetric stretching vibration. Three Raman bands at 898, 908 and 947 cm⁻¹ are assigned to the ν₃(AsO₃)³⁻ antisymmetric stretching vibration. The observation of multiple antisymmetric stretching vibrations suggest that the (AsO₃)³⁻ units are not equivalent in the molecular structure of finnemanite. Two Raman bands at 383 and 399 cm⁻¹are assigned to the ν₂(AsO₃)³⁻ bending modes. Density functional theory enabled calculation of the position of AsO₃²⁻ symmetric stretching mode at 839 cm⁻¹, the antisymmetric stretching mode at 813 cm⁻¹ and the deformation mode at 449 cm⁻¹. Raman bands are observed at 115, 145, 162, 176, 192, 216 and 234 cm⁻¹ as well. The two most intense bands are observed at 176 and 192 cm⁻¹. These bands are assigned to PbCl stretching vibrations and result from transverse/longitudinal splitting. The bands at 145 and 162 cm⁻¹ may be assigned to Cl Pb Cl bending modes. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl carbonate mineral voglite

Raman spectroscopy, complemented with infrared spectroscopy, was used to study the uranyl carbonate mineral voglite. The mineral has the formula Ca₂Cu²⁺ [(UO₂)(CO₃)₃](CO₃)^•6H₂O, and bands attributed to these vibrating units are readily identified in the Raman spectrum. Symmetric stretching modes at 836 and 1094 cm⁻¹ are assigned to ν₁(UO₂)²⁺ and ν₁(CO₃)²⁻ units, respectively. The ν₃ antisymmetric stretching modes of (UO₂)²⁺ are not observed in the Raman spectrum but may be readily observed in the infrared spectrum at 898 cm⁻¹. The ν₃ antisymmetric stretching mode of (CO₃)²⁻ is observed in the Raman spectrum at 1369 cm⁻¹ as a low intensity band as is also the ν₃(CO₃)²⁻ infrared modes at 1362, 1425, 1509 and 1566 cm⁻¹. No ν₂(CO₃)²⁻ Raman bending modes are observed for voglite. The Raman band at 749 cm⁻¹ and the two infrared bands at 747 and 709 cm⁻¹ are assigned to the ν₄(CO₃)²⁻ bending modes. U O bond and O H…O bond lengths in the structure of voglite were inferred from the infrared and Raman spectra. Copyright © 2007 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the mixed anion sulphate–arsenate mineral parnauite Cu9[(OH)10|SO4|(AsO4)2]·7H2O

The mixed anion mineral parnauite Cu₉[(OH)₁₀|SO₄|(AsO₄)₂]·7H₂O has been studied by Raman spectroscopy. Characteristic bands associated with arsenate, sulphate and hydroxyl units are identified. Broad bands are observed and are resolved into component bands. Two intense bands at 859 and 830 cm⁻¹ are assigned to the ν₁ (AsO₄)³⁻ symmetric stretching and ν₃ (AsO₄)³⁻ antisymmetric stretching modes. The comparatively sharp band at 976 cm⁻¹ is assigned to the ν₁ (SO₄)²⁻ symmetric stretching mode and a broad‐spectral profile centered upon 1097 cm⁻¹ is attributed to the ν₃ (SO₄)²⁻ antisymmetric stretching mode. A comparison of the Raman spectra is made with other arsenate‐bearing minerals such as carminite, clinotyrolite, kankite, tilasite and pharmacosiderite. Copyright © 2009 John Wiley & Sons, Ltd.     

A Raman spectroscopic study of copiapites Fe2+Fe3+(SO4)6(OH)2 · 20H2O: environmental implications

Raman spectroscopy has been used to study selected mineral samples of the copiapite group. Copiapite (Fe²⁺Fe³⁺(SO₄)₆(OH)₂ · 20H₂O) is a secondary mineral formed through the oxidation of pyrite. Minerals of the copiapite group have the general formula AFe₄(SO₄)₆(OH)₂ · 20H₂O, where A has a + 2 charge and can be either magnesium, iron, copper, calcium and/or zinc. The formula can also be B_2/3Fe₄(SO₄)₆(OH)₂ · 20H₂O, where B has a + 3 charge and may be either aluminium or iron. For each mineral, two Raman bands are observed at around 992 and 1029 cm⁻¹, assigned to the (SO₄)²⁻ν₁ symmetric stretching mode. The observation of two bands provides evidence for the existence of two non‐equivalent sulfate anions in the mineral structure. Three Raman bands at 1112, 1142 and 1161 cm⁻¹ are observed in the Raman spectrum of copiapites, indicating a reduction of symmetry of the sulfate anion in the copiapite structure. This reduction in symmetry is supported by multiple bands in the ν₂ and ν₄(SO₄)²⁻ spectral regions. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectrum of decrespignyite [(Y,REE)4Cu(CO3)4Cl(OH)5·2H2O] and its relation with those of other halogenated carbonates including bastnasite,hydroxybastnasite, parisite and northupite

Raman spectroscopy complemented with infrared spectroscopy has been used to study the rare‐earth‐based mineral decrespignyite [(Y,REE)₄Cu(CO₃)₄Cl(OH)₅· 2H₂O] and the spectrum compared with the Raman spectra of a series of selected natural halogenated carbonates from different origins including bastnasite, parisite and northupite. The Raman spectrum of decrespignyite displays three bands at 1056, 1070 and 1088 cm⁻¹ attributed to the CO₃²⁻ symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of the CO₃²⁻ symmetric stretching vibration varies with the mineral composition. The Raman spectrum of decrespignyite shows bands at 1391, 1414, 1489 and 1547 cm⁻¹, whereas the Raman spectra of bastnasite, parisite and northupite show a single band at 1433, 1420 and 1554 cm⁻¹, respectively, assigned to the ν₃ (CO₃)²⁻ antisymmetric stretching mode. The observation of additional Raman bands for the ν₃ modes for some halogenated carbonates is significant in that it shows distortion of the carbonate anion in the mineral structure. Four Raman bands are observed at 791, 815, 837 and 849 cm⁻¹, which are assigned to the (CO₃)²⁻ν₂ bending modes. Raman bands are observed for decrespignyite at 694, 718 and 746 cm⁻¹ and are assigned to the (CO₃)²⁻ν₄ bending modes. Raman bands are observed for the carbonate ν₄ in‐phase bending modes at 722 cm⁻¹ for bastnasite, 736 and 684 cm⁻¹ for parisite and 714 cm⁻¹ for northupite. Multiple bands are observed in the OH stretching region for decrespignyite, bastnasite and parisite, indicating the presence of water and OH units in the mineral structure. Copyright © 2011 John Wiley & Sons, Ltd.     

A Raman spectroscopic study of the different vanadate groups in solid‐state compounds—model case: mineral phases vésigniéite [BaCu3(VO4)2(OH)2] and volborthite [Cu3V2O7(OH)2·2H2O]

Raman spectroscopy has been used to study vanadates in the solid state. The molecular structure of the vanadate minerals vésigniéite [BaCu₃(VO₄)₂(OH)₂] and volborthite [Cu₃V₂O₇(OH)₂·2H₂O] have been studied by Raman spectroscopy and infrared spectroscopy. The spectra are related to the structure of the two minerals. The Raman spectrum of vésigniéite is characterized by two intense bands at 821 and 856 cm⁻¹ assigned to ν₁ (VO₄)³⁻ symmetric stretching modes. A series of infrared bands at 755, 787 and 899 cm⁻¹ are assigned to the ν₃ (VO₄)³⁻ antisymmetric stretching vibrational mode. Raman bands at 307 and 332 cm⁻¹ and at 466 and 511 cm⁻¹ are assigned to the ν₂ and ν₄ (VO₄)³⁻ bending modes. The Raman spectrum of volborthite is characterized by the strong band at 888 cm⁻¹, assigned to the ν₁ (VO₃) symmetric stretching vibrations. Raman bands at 858 and 749 cm⁻¹ are assigned to the ν₃ (VO₃) antisymmetric stretching vibrations; those at 814 cm⁻¹ to the ν₃ (VOV) antisymmetric vibrations; that at 508 cm⁻¹ to the ν₁ (VOV) symmetric stretching vibration and those at 442 and 476 cm⁻¹ and 347 and 308 cm⁻¹ to the ν₄ (VO₃) and ν₂ (VO₃) bending vibrations, respectively. The spectra of vésigniéite and volborthite are similar, especially in the region of skeletal vibrations, even though their crystal structures differ. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the magnesium‐carbonate minerals—artinite and dypingite

Magnesium minerals are important in the understanding of the concept of geosequestration. The two hydrated hydroxy magnesium‐carbonate minerals artinite and dypingite were studied by Raman spectroscopy. Intense bands are observed at 1092 cm⁻¹ for artinite and at 1120 cm⁻¹ for dypingite, attributed ν₁ symmetric stretching mode of CO₃²⁻. The ν₃ antisymmetric stretching vibrations of CO₃²⁻ are extremely weak and are observed at 1412 and 1465 cm⁻¹ for artinite and at 1366, 1447 and 1524 cm⁻¹ for dypingite. Very weak Raman bands at 790 cm⁻¹ for artinite and 800 cm⁻¹ for dypingite are assigned to the CO₃²⁻ν₂ out‐of‐plane bend. The Raman band at 700 cm⁻¹ of artinite and at 725 and 760 cm⁻¹ of dypingite are ascribed to CO₃²⁻ν₂ in‐plane bending mode. The Raman spectrum of artinite in the OH stretching region is characterised by two sets of bands: (1) an intense band at 3593 cm⁻¹ assigned to the MgOH stretching vibrations and (2) the broad profile of overlapping bands at 3030 and 3229 cm⁻¹ attributed to water stretching vibrations. X‐ray diffraction studies show that the minerals are disordered. This is reflected in the difficulty of obtaining Raman spectra of reasonable quality, and explains why the Raman spectra of these minerals have not been previously or sufficiently described. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the multi‐anion uranyl mineral schroeckingerite

Raman spectroscopy complemented with infrared (IR) spectroscopy has been used to study the mineral schroeckingerite. The mineral is a multi‐anion mineral and has (UO₂)²⁺, (SO₄)²⁻ and (CO₃)²⁻ units in its structure, and bands attributed to these vibrating units are readily identified in the Raman spectra. Symmetric stretching modes at 815, 983 and 1092 cm⁻¹ are assigned to (UO₂)²⁺, (SO₄)²⁻ and (CO₃)²⁻ units, respectively. The antisymmetric stretching modes of (UO₂)²⁺, (SO₄)²⁻ are not observed in the Raman spectra but may be readily observed in the IR spectrum at 898 and 1180 cm⁻¹. The antisymmetric stretching mode of (CO₃)²⁻ is observed in the Raman spectrum at 1374 cm⁻¹, as is also the ν₄ (CO₃)²⁻ bending modes at 742 and 707 cm⁻¹. No ν₂ (CO₃)²⁻ bending modes are observed in the Raman spectrum of schroeckingerite. All the spectroscopic evidence points to a highly ordered structure of this mineral. Copyright © 2007 John Wiley & Sons, Ltd.     

Raman spectroscopy of uranopilite of different origins—implications for molecular structure

Uranopilite, [(UO₂)₆(SO₄)O₂(OH)₆(H₂O)₆](H₂O)₈, the composition of which may vary, can be understood as a complex hydrated uranyl oxyhydroxy sulfate. The structure of uranopilite from different locations has been studied by Raman spectroscopy at 298 and 77 K. A single intense band at 1009 cm⁻¹ assigned to the ν₁ (SO₄)²⁻ symmetric stretching mode shifts to higher wavenumbers at 77 K. Three low‐intensity bands are observed at 1143, 1117 and 1097 cm⁻¹. These bands are attributed to the (SO₄)²⁻ ν₃ anti‐symmetric stretching modes. Multiple bands provide evidence that the symmetry of the sulfate anion in the uranopilite structure is lowered. Three bands are observed in the region 843 to 816 cm⁻¹ in both the 298 and 77 K spectra and are attributed to the ν₁ symmetric stretching modes of the (UO₂)²⁺ units. Multiple bands prove the symmetry reduction of the UO₂ ion. Multiple OH stretching modes prove a complex arrangement of OH groupings and hydrogen bonding in the crystal structure. A series of infrared bands not observed in the Raman spectra are found at 1559, 1540, 1526 and 1511 cm⁻¹ attributed to δ UOH bending modes. U‐O bond lengths in uranyl and O H/dotbondO bond lengths are calculated and compared with those from X‐ray single crystal structure analysis. The Raman spectra of uranopilites of different origins show subtle differences, proving that the spectra are origin‐ and sample‐dependent. Hydrogen‐bonding network and its arrangement in the crystal structure play an important role in the origin and stability of uranopilite. Copyright © 2006 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the multi‐anion mineral dixenite CuMn2+14Fe3+(AsO3)5(SiO4)2(AsO4)(OH)6

The mixed anion mineral dixenite has been studied by Raman spectroscopy, complemented with infrared spectroscopy. The Raman spectrum of dixenite shows bands at 839 and 813 cm⁻¹ assigned to the (AsO₃)³⁻ symmetric and antisymmetric stretching modes. The most intense Raman band of dixenite is the band at 526 cm⁻¹ and is assigned to the ν₂ AsO₃³⁻ bending mode. DFT calculations enabled the calculation of 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. The Raman bands at 1026 and 1057 cm⁻¹ are assigned to the SiO₄²⁻ symmetric stretching vibrations and those at 1349 and 1386 cm⁻¹ to the SiO₄²⁻ antisymmetric stretching vibrations. Both Raman and infrared spectra indicate the presence of water in the structure of dixenite. This brings into question the commonly accepted formula of dixenite as CuMn²⁺₁₄Fe³⁺(AsO₃)₅(SiO₄)₂(AsO₄)(OH)₆. The formula may be better written as CuMn²⁺₁₄Fe³⁺(AsO₃)₅(SiO₄)₂(AsO₄)(OH)₆·xH₂O. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the hydrogen‐arsenate mineral pharmacolite Ca(AsO3OH)·2H2O—implications for aquifer and sediment remediation

The removal of arsenate anions from aqueous media, sediments and wasted soils is of environmental significance. The reaction of gypsum with the arsenate anion results in pharmacolite mineral formation, together with related minerals. Raman and infrared (IR) spectroscopy have been used to study the mineral pharmacolite Ca(AsO₃OH)· 2H₂O. The mineral is characterised by an intense Raman band at 865 cm⁻¹ assigned to the ν₁ (AsO₃)²⁻ symmetric stretching mode. The equivalent IR band is found at 864 cm⁻¹. The low‐intensity Raman bands in the range from 844 to 886 cm⁻¹ provide evidence for ν₃ (AsO₃) antisymmetric stretching vibrations. A series of overlapping bands in the 300‐450 cm⁻¹ region are attributed to ν₂ and ν₄ (AsO₃) bending modes. Prominent Raman bands at around 3187 cm⁻¹ are assigned to the OH stretching vibrations of hydrogen‐bonded water molecules and the two sharp bands at 3425 and 3526 cm⁻¹ to the OH stretching vibrations of only weakly hydrogen‐bonded hydroxyls in (AsO₃OH)²⁻ units. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman and mid‐IR spectroscopic study of the magnesium carbonate minerals—brugnatellite and coalingite

Two hydrated hydroxy magnesium carbonate minerals brugnatellite and coalingite with a hydrotalcite‐like structure were studied by Raman spectroscopy. Intense bands are observed at 1094 cm⁻¹ for brugnatellite and at 1093 cm⁻¹ for coalingite attributed to the CO₃²⁻ν₁ symmetric stretching mode. Additional low intensity bands are observed at 1064 cm⁻¹. The existence of two symmetric stretching modes is accounted for in terms of different anion structural arrangements. Very low intensity bands at 1377 and 1451 cm⁻¹ are observed for brugnatellite, and the Raman spectrum of coalingite displays two bands at 1420 and 1465 cm⁻¹ attributed to the (CO₃)²⁻ν₃ antisymmetric stretching modes. Very low intensity bands at 792 cm⁻¹ for brugnatellite and 797 cm⁻¹ for coalingite are assigned to the CO₃²⁻ out‐of‐plane bend (ν₂). X‐ray diffraction studies by other researchers have shown that these minerals are disordered. This is reflected in the difficulty of obtaining Raman spectra of reasonable quality and explains why the Raman spectra of these minerals have not been previously or sufficiently described. A comparison is made with the Raman spectra of other hydrated magnesium carbonate minerals. Copyright © 2008 John Wiley & Sons, Ltd.