Raman spectroscopic study of the uranyl sulphate mineral jáchymovite (UO2)8(SO4)(OH)14· 13H2O

Raman spectra of jáchymovite, (UO₂)₈(SO₄)(OH)₁₄·13H₂O, were studied, complemented with infrared spectra, and compared with published Raman and infrared spectra of uranopilite, [(UO₂)₆(SO₄)O₂(OH)₆(H₂O)₆]·6H₂O. Bands related to the stretching and bending vibrations of (UO₂)²⁺, (SO₄)²⁻, (OH)⁻ and water molecules were assigned. 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 uranyl selenite mineral demesmaekerite Pb2Cu5(UO2)2(SeO3)6(OH)6·2H2O

The Raman spectrum of the uranyl selenite mineral demesmaekerite was studied, complemented by the infrared spectrum and tentatively interpreted. The observed bands were attributed to the stretching and bending vibrations of (UO₂)²⁺, (SeO₃)²⁻ and OH groupings. U O bond lengths in uranyl and O H···O hydrogen bond lengths were calculated from Raman and/or infrared spectra and compared with published data. Copyright © 2008 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 mineral guilleminite Ba(UO2)3(SeO3)2(OH)4·3H2O

The Raman spectrum of the mineral guilleminite Ba[(UO₂)₃O₂(SeO₃)₂](H₂O)₃ was studied and complemented by the infrared spectrum of this mineral. Both spectra were interpreted and compared with the spectra of marthozite, larisaite, haynesite and piretite, all of which should have the same phosphuranylite anion sheet topology. The presence of symmetrically distinct water molecules and hydrogen bonds was inferred from the spectra. This is in agreement with the crystal structural analysis of guilleminite. U O bond lengths in uranyl and O H···O hydrogen bond lengths were calculated from the Raman and/or infrared spectra of guilleminite. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl carbonate mineral zellerite

Raman and infrared spectra of the uranyl mineral zellerite, Ca[(UO₂)(CO₃)₂(H₂O)₂]·3H₂O, were measured and tentatively interpreted. U O bond in uranyl and O H···O hydrogen bonds were calculated from the vibrational spectra. The presence of structurally nonequivalent water molecules in the crystal structure of zellerite was inferred. A proposed chemical formula of zellerite is supported. Raman bands at 3514, 3375 and 2945 cm⁻¹and broad infrared bands at 3513, 3396 and 3326 cm⁻¹ are related to the ν OH stretching vibrations of hydrogen‐bonded water molecules. Observed wavenumbers of these vibrations prove that in fact hydrogen bonds participate in the crystal structure of zellerite. The presence of two bands at 1618 and 1681 cm⁻¹ proves structurally distinct and nonequivalent water molecules in the crystal structure of zellerite. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman microscopy of the mixite mineral BiCu6(AsO4)3(OH)6·3H2O from the Czech Republic

Raman microscopy of the mixite mineral BiCu₆(AsO₄)₃(OH)₆·3H₂O from Jáchymov and from Smrkovec (both Czech Republic) has been used to study their molecular structure. The presence of (AsO₄)³⁻, (AsO₃OH)²⁻, (PO₄)³⁻ and (PO₃OH)²⁻ units, as well as molecular water and hydroxyl ions, was inferred. O H···O hydrogen bond lengths were calculated from the Raman and infrared spectra using Libowitzky's empirical relation. Small differences in the Raman spectra between both samples were observed and attributed to compositional and hydrogen‐bonding network differences. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl titanate mineral brannerite (U,Ca,Y,Ce)2(Ti,Fe)2O6:effect of metamictisation

Raman spectra of the uranyl titanate mineral brannerite were analysed and related to the mineral structure. A comparison is made with the Raman spectra of uranyl oxyhydroxide hydrates. The observed bands are attributed to the TiO and (UO₂)²⁺ stretching and bending vibrations, U OH bending vibrations, as well as H₂O and (OH)⁻ stretching, bending and libration modes. U O bond lengths in uranyls and O H···O bond lengths were calculated from the wavenumbers assigned to the stretching vibrations. Raman bands of brannerite are in harmony with those of the uranyl oxyhydroxides. The mineral brannerite is metamict, as is evidenced by the intensity of the UO stretching and bending modes being of lower intensity than expected and with bands that are significantly broader. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl mineral,compreignacite, K2[(UO2)3O2(OH)3]2·7H2O

Raman spectra of the uranyl oxyhydroxy‐hydrated mineral compreignacite, K₂[(UO₂)₃O₂(OH)₃]₂·7H₂O, were measured and interpreted. Observed bands were attributed to the stretching and bending vibrations of uranyl units, molecular water and hydroxyl ions. U O bond lengths in uranyl and O HO hydrogen bond lengths were inferred from the spectra and compared with those from the X‐ray single crystal structure data. The importance of this spectroscopic study rests with the ability to analyze very small amounts of the mineral. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl selenite mineral marthozite Cu[(UO2)3(SeO3)2O2]·8H2O

The mineral marthozite, a uranyl selenite, has been characterised by Raman spectroscopy at 298 K. The bands at 812 and 797 cm⁻¹ were assigned to the symmetric stretching modes of the (UO₂)²⁺ and (SeO₃)²⁻ units, respectively. These values gave the calculated U O bond lengths in uranyl of 1.799 and/or 1.814 Å. Average U O bond length in uranyl is 1.795 Å, inferred from the X‐ray single crystal structure analysis of marthozite by Cooper and Hawthorne. The broad band at 869 cm⁻¹ was assigned to the ν₃ antisymmetric stretching mode of the (UO₂)²⁺ (calculated U O bond length 1.808 Å). The band at 739 cm⁻¹ was attributed to the ν₃ antisymmetric stretching vibration of the (SeO₃)²⁻ units. The ν₄ and the ν₂ vibrational modes of the (SeO₃)²⁻ units were observed at 424 and 473 cm⁻¹. Bands observed at 257, and 199 and 139 cm⁻¹ were assigned to OUO bending vibrations and lattice vibrations, respectively. O H···O hydrogen bond lengths were inferred using Libowiztky's empirical relation. The infrared spectrum of marthozite was studied for complementation. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopy of hydrogen‐arsenate group (AsO3OH) in solid‐state compounds: copper mineral phase geminite Cu(AsO3OH)·H2O from different geological environments

The participation of hydrogen‐arsenate group (AsO₃OH)²⁻ in solid‐state compounds may serve as a model example for explaining and clarifying the behaviour of As and other elements during weathering processes in natural environment. The mineral geminite, a hydrated hydrogen‐arsenate mineral of ideal formula Cu(AsO₃OH)·H₂O, has been studied by Raman and infrared spectroscopies. Two samples of geminite of different origin were investigated and the spectra proved quite similar. In the Raman spectra of geminite, six bands are observed at 741, 812, 836, 851, 859 and 885 cm⁻¹ (Salsigne, France), and 743, 813, 843, 853, 871 and 885 cm⁻¹ (Jáchymov, Czech Republic). The band at 851/853 cm⁻¹ is assigned to the ν₁ (AsO₃OH)²⁻ symmetric stretching mode; the other bands are assigned to the ν₃ (AsO₃OH)²⁻ split triply degenerate antisymmetric stretching mode. Raman bands at 309, 333, 345 and 364/310, 333 and 345 cm⁻¹ are attributed to the ν₂ (AsO₃OH)²⁻ bending mode, and a set of higher wavenumber bands (in the range 400–500 cm⁻¹) is assigned to the ν₄ (AsO₃OH)²⁻ split triply degenerate bending mode. A very complex set of overlapping bands is observed in both the Raman and infrared spectra. Raman bands are observed at 2289, 2433, 2737, 2855, 3235, 3377, 3449 and 3521/2288, 2438, 2814, 3152, 3314, 3448 and 3521 cm⁻¹. Two Raman bands at 2289 and 2433/2288 and 2438 cm⁻¹ are ascribed to the strong hydrogen bonded water molecules. The Raman bands at 3235, 3305 and 3377/3152 and 3314 cm⁻¹ may be assigned to the ν OH stretching vibrations of water molecules. Two bands at 3449 and 3521/3448 and 3521 cm⁻¹ are assigned to the OH stretching vibrations of the (AsO₃OH)²⁻ units. The lengths of the O H···O hydrogen bonds vary in the range 2.60–2.94 Å (Raman) and 2.61–3.07 Å (infrared). Two Raman and infrared bands in the region of the bending vibrations of the water molecules prove that structurally non‐equivalent water molecules are present in the crystal structure of geminite. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman and infrared spectroscopic study of the molybdate‐containing uranyl mineral calcurmolite

Raman and infrared spectra of calcurmolite were recorded and interpreted from the uranium and molybdenum polyhedra, water molecules and hydroxyls point of view. U O bond lengths in uranyl and Mo O bond lengths in MoO₆ octahedra were calculated and O H…O bond lengths were inferred from the spectra. The mineral calcurmolite is characterised by bands assigned to the vibrations of the UO₂ units. These units provide intense Raman bands at 930, 900 and 868 and 823 cm⁻¹. These bands are attributed to the anti‐symmetric and symmetric stretching modes of the UO₂ units, respectively. Raman bands at 794, 700, 644, 378 and 354 cm⁻¹ are attributed to vibrations of the MoO₄ units. The bands at 693 and 668 cm⁻¹ are assigned to the anti‐symmetric and symmetric A_g modes of the terminal MO₂ units. Similar bands are observed at 797 and 773 cm⁻¹ for koechlinite and 798 and 775 cm⁻¹ for lindgrenite. It is probable that some of the bands in the low wavenumber region are attributable to the bending modes of MO₂ units. Copyright © 2008 John Wiley & Sons, Ltd.     

A Raman spectroscopic study of the uranyl mineral rutherfordine—revisited

The molecular structure of the uranyl mineral rutherfordine has been investigated by the measurement of the near‐infrared (NIR) and Raman spectra and complemented with infrared spectra including their interpretation. The spectra of rutherfordine show the presence of both water and hydroxyl units in the structure as evidenced by IR bands at 3562 and 3465 cm⁻¹ (OH) and 3343, 3185 and 2980 cm⁻¹ (H₂O). Raman spectra show the presence of four sharp bands at 3511, 3460, 3329 and 3151 cm⁻¹. Corresponding molecular water bending vibrations were only observed in both Raman and infrared spectra of one of two studied rutherfordine samples. The second rutherfordine sample studied contained only hydroxyl ions in the equatorial uranyl plane and did not contain any molecular water. The infrared spectra of the (CO₃)²⁻ units in the antisymmetric stretching region show complexity with three sets of carbonate bands observed. This combined with the observation of multiple bands in the (CO₃)²⁻ bending region in both the Raman and IR spectra suggests that both monodentate and bidentate (CO₃)²⁻ units may be present in the structure. This cannot be exactly proved and inferred from the spectra; however, it is in accordance with the X‐ray crystallographic studies. Complexity is also observed in the IR spectra of (UO₂)²⁺ antisymmetric stretching region and is attributed to non‐identical UO bonds. U O bond lengths were calculated using wavenumbers of the ν₃ and ν₁ (UO₂)²⁺ and compared with data from X‐ray single crystal structure analysis of rutherfordine. Existence of solid solution having a general formula (UO₂)(CO₃)_1−x(OH)_2x.yH₂O (x, y ≥ 0) is supported in the crystal structure of rutherfordine samples studied. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl titanate mineral euxenite (Y,Ca,U,Ce,Th) (Nb,Ta,Ti)2O6

Raman spectra of the uranyl titanate mineral euxenite were analysed and related to the mineral structure. A comparison is made with the Raman spectra of uranyl oxyhydroxide hydrates. The observed bands are attributed to the Ti O and (UO₂)²⁺ stretching and bending vibrations, as well as lattice vibrations of rare‐earth ions. The Raman bands of euxenite are in harmony with those of the uranyl oxyhydroxides. The mineral euxenite is metamict as is evidenced by the intensity of the U O stretching and bending modes, which are of lower intensity than expected, and with bands that are significantly broader. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl phosphate minerals phosphuranylite and yingjiangite

Raman spectra of phosphuranylite and yingjiangite were measured and interpreted, and compared with the published infrared spectra of both minerals. U O bond lengths were calculated using the Bartlett–Cooney empirical relations and the O HċO hydrogen bond lengths were inferred on the basis of Libowitzky's empirical relation. The presence of oxonium and (H₃O)⁺ ions, expected from the single crystal structure analysis of phosphuranylite, was not inferred from the Raman spectra. It was assumed that phosphuranylite and yingjiangite are identical and the name yingjiangite should be discarded because the name phosphuranylite has priority. Copyright © 2007 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl oxyhydroxide hydrates: becquerelite,billietite, curite,schoepite and vandendriesscheite

Raman and infrared spectra of five uranyl oxyhydroxide hydrates, becquerelite, billietite, curite, schoepite and vandendriesscheite, are reported. The observed bands are attributed to the (UO₂)²⁺ stretching and bending vibrations, U OH bending vibrations and H₂O and (OH)⁻ stretching, bending and libration modes. The U O bond lengths in uranyls and the O H···O bond lengths are calculated from the wavenumbers assigned to the stretching vibrations. They are close to the values inferred and/or predicted from the X‐ray single‐crystal structure. The complex hydrogen‐bonding network arrangement was proved in the structures of all the minerals studied. This hydrogen bonding contributes to the stability of these uranyl minerals. Copyright © 2006 John Wiley & Sons, Ltd. John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl tellurite mineral moctezumite PbUO2(TeO3)2

The uranyl tellurite mineral moctezumite, Pb(UO₂)(TeO₃)₂, was studied by Raman spectroscopy and complemented with infrared spectroscopy. The presence of the stretching and bending vibrations of uranyl (UO₂)²⁺ and tellurite (TeO₃)²⁻ ions was inferred, and the observed bands were assigned to uranyl and tellurite units vibrations. U O bond lengths calculated from the spectra with two empirical relations are close to those inferred from the X‐ray single‐crystal structure of moctezumite. Copyright © 2008 John Wiley & Sons, Ltd.     

A Raman and infrared spectroscopic study of Ca2+ dominant members of the mixite group from the Czech Republic

The minerals of the mixite group—zálesíite CaCu₆[(AsO₄)₂(AsO₃OH)(OH)₆]·3H₂O from abandoned uranium deposit Zálesí, Czech Republic and calciopetersite CaCu₆[(PO₄)₂(PO₃OH)(OH)₆]·3H₂O from a quarry near Domašov na Bystřicí, northern Moravia, Czech Republic—were studied by Raman and infrared spectroscopy. The observed bands were assigned to the stretching and bending vibrations of (AsO₄)³⁻ and (AsO₃OH)²⁻ ions in zálesíite, and (PO₄)³⁻ and (PO₃OH)²⁻ in calciopetersite, and to molecular water, hydroxyl ions, and Cu‐(O,OH) units in both minerals. O H···O hydrogen‐bond lengths in zálesíite and calciopetersite structures were calculated with Libowitzky's empirical relation. Copyright © 2010 John Wiley & Sons, Ltd.     

XRD studies,vibrational spectra,and molecular structure of 1H‐imidazo [4,5‐b]pyridine based on DFT quantum chemical calculations

The molecular structures and vibrational properties of 1H‐imidazo[4,5‐b]pyridine in its monomeric and dimeric forms are analyzed and compared to the experimental results derived from the X‐ray diffraction (XRD), infrared (IR), and Raman studies. The theoretical data are discussed on the basis of density functional theory (DFT) quantum chemical calculations using Lee–Yang–Parr correlation functional (B3LYP) and 6‐31G(d,p) basis. This compound crystallizes in orthorhombic structure, space group Pna2₁(C_2v⁹) and Z = 4. The planar conformation of the skeleton and presence of the N H···N hydrogen bond was found to be characteristic for the studied system. The temperature dependence of IR and Raman modes was studied in the range 4–294 K and 8–295 K, respectively. The normal modes, which are unique for the imidazopyridine derivatives are identified. Copyright © 2009 John Wiley & Sons, Ltd.     

Effects of metal ion on the water structure studied by the Raman O?H stretching spectrum

Raman spectra in the O H stretching region of aqueous salt solutions were measured and compared, and the effects of metal ions on water structure deduced. The effects of alkali ions, alkaline ions or the first‐row transition metals on water structure were found to be similar. Differences of metal ionic effects on water structure exist among Na⁺, Mg²⁺ and Al³⁺, and between Ca²⁺ and Mn²⁺ and Al³⁺ and Fe³⁺. The factors that influence the metal ionic effects on the water structure are the ionic charge, the outmost electronic structure and ionic size, the ionic charge being the most important. With a five‐component Gaussian deconvolution of the Raman spectra of the aqueous solutions of NaCl, MgCl₂, AlCl₃ and FeCl₃ with concentrations of 0 to ∼1mol/l, the ionic effects were found to be similar on the bands at 3233, 3393, 3511 and 3628 cm⁻¹, but different on the band at 3051 cm⁻¹. With increasing polarization of the metal ion, the band at 3051 cm⁻¹, due to strong hydrogen bonding, increases. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl carbonate mineral čejkaite and its comparison with synthetic trigonal Na4[UO2(CO3)3]

Raman and infrared spectroscopies were used to characterise two samples of triclinic čejkaite Na₄[UO₂(CO₃)₃] and its synthetic trigonal analogue. The ν₃ (UO₂)²⁺ mode is not Raman active, whereas both the ν₃ and ν₁ (UO₂)²⁺ modes are infrared active. U O bond lengths in uranyls were calculated from the spectra obtained and compared with bond lengths derived from crystal structure analyses. From the higher number of bands related to the uranyl and carbonate vibrations, the presence of symmetrically distinct (UO₂)²⁺ and (CO₃)²⁻ units in both structures is proposed. Copyright © 2009 John Wiley & Sons, Ltd.