A vibrational spectroscopic study of the silicate mineral lomonosovite Na5Ti2(Si2O7)(PO4)O2

The mineral lomonosovite has been studied using a combination of scanning electron microscopy with energy dispersive X-ray analysis and vibrational spectroscopy. Qualitative chemical analysis gave Si, P, Na and Ti as the as major elements with small amounts of Mn, Ca, Fe and Al. The mineral lomonosovite has a formula Na5Ti2(Si2O7)(PO4)O2. Raman bands observed at 909, 925 and 939 cm−1 are associated with phosphate units. Raman bands found at 975, 999, 1070, 1080 and 1084 cm−1 are attributed to siloxane stretching vibrations. The observation of multiple bands in both the phosphate stretching and bending regions supports the concept that the symmetry of the phosphate anion in the structure of lomonosovite is significantly reduced. Infrared spectroscopy identifies bands in the water stretching and bending regions, thus suggesting that water is involved with the structure of lomonosovite either through adsorption on the surface or by bonding to the phosphate units.

Vibrational spectroscopy of the borate mineral priceite : implications for the molecular structure

Priceite is a calcium borate mineral and occurs as white crystals in the monoclinic pyramidal crystal system. We have used a combination of Raman spectroscopy with complimentary infrared spectroscopy and scanning electron microscopy with Energy-dispersive X-ray Spectroscopy (EDS) to study the mineral priceite. Chemical analysis shows a pure phase consisting of B and Ca only. Raman bands at 956, 974, 991, and 1019 cm−1 are assigned to the BO stretching vibration of the B10O19 units. Raman bands at 1071, 1100, 1127, 1169, and 1211 cm−1 are attributed to the BOH in-plane bending modes. The intense infrared band at 805 cm−1 is assigned to the trigonal borate stretching modes. The Raman band at 674 cm−1 together with bands at 689, 697, 736, and 602 cm−1 are assigned to the trigonal and tetrahedral borate bending modes. Raman spectroscopy in the hydroxyl stretching region shows a series of bands with intense Raman band at 3555 cm−1 with a distinct shoulder at 3568 cm−1. Other bands in this spectral region are found at 3221, 3385, 3404, 3496, and 3510 cm−1. All of these bands are assigned to water stretching vibrations. The observation of multiple bands supports the concept of water being in different molecular environments in the structure of priceite. The molecular structure of a natural priceite has been assessed using vibrational spectroscopy.

An SEM, EDS and vibrational spectroscopic study of the silicate mineral meliphanite (Ca,Na)2Be[(Si,Al)2O6(F,OH)]

The mineral meliphanite (Ca,Na)2Be[(Si,Al)2O6(F,OH)] is a crystalline sodium calcium beryllium silicate which has the potential to be used as piezoelectric material and for other ferroelectric applications. The mineral has been characterized by a combination of scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS) and vibrational spectroscopy. EDS analysis shows a material with high concentrations of Si and Ca and low amounts of Na, Al and F. Beryllium was not detected. Raman bands at 1016 and 1050 cm−1 are assigned to the SiO and AlOH stretching vibrations of three dimensional siloxane units. The infrared spectrum of meliphanite is very broad in comparison with the Raman spectrum. Raman bands at 472 and 510 cm−1 are assigned to OSiO bending modes. Raman spectroscopy identifies bands in the OH stretching region. Raman spectroscopy with complimentary infrared spectroscopy enables the characterization of the silicate mineral meliphanite.

SEM, EDX and vibrational spectroscopic study of the mineral tunisite NaCa2Al4(CO3)4Cl(OH)8

The mineral tunisite has been studied by using a combination of scanning electron microscopy with energy dispersive X-ray fluorescence and vibrational spectroscopy. Chemical analysis shows the presence of Na, Ca, Al and Cl. SEM shows a pure single phase. An intense Raman band at 1127 cm−1 is assigned to the carbonate ν1 symmetric stretching vibration and the Raman band at 1522 cm−1 is assigned to the ν3 carbonate antisymmetric stretching vibration. Infrared bands are observed in similar positions. Multiple carbonate bending modes are found. Raman bands attributable to AlO stretching and bending vibrations are observed. Two Raman bands at 3419 and 3482 cm−1 are assigned to the OH stretching vibrations of the OH units. Vibrational spectroscopy enables aspects of the molecular structure of the carbonate mineral tunisite to be assessed.

SEM, EDS and vibrational spectroscopic study of dawsonite NaAl(CO3)(OH)2

In this work we have studied the mineral dawsonite by using a combination of scanning electron microscopy with EDS and vibrational spectroscopy. Single crystals show an acicular habitus forming aggregates with a rosette shape. The chemical analysis shows a phase composed of C, Al, and Na. Two distinct Raman bands at 1091 and 1068 cm−1 are assigned to the CO32− ν1 symmetric stretching mode. Multiple bands are observed in both the Raman and infrared spectra in the antisymmetric stretching and bending regions showing that the symmetry of the carbonate anion is reduced and in all probability the carbonate anions are not equivalent in the dawsonite structure. Multiple OH deformation vibrations centred upon 950 cm−1 in both the Raman and infrared spectra show that the OH units in the dawsonite structure are non-equivalent. Raman bands observed at 3250, 3283 and 3295 cm−1 are assigned to OH stretching vibrations. The position of these bands indicates strong hydrogen bonding of the OH units in the dawsonite structure. The formation of the mineral dawsonite has the potential to offer a mechanism for the geosequestration of greenhouse gases.

A vibrational spectroscopic study of the arsenate minerals cobaltkoritnigite and koritnigite

Raman spectra of two well-defined types of cobaltkoritnigite and koritnigite crystals were recorded and interpreted. Significant differences in the Raman spectra of cobaltkoritnigite and koritnigite were observed. Observed Raman bands were attributed to the (AsO3OH)2− stretching and bending vibrations, stretching and bending vibrations of water molecules and hydroxyl ions. Both Raman and infrared spectra of cobaltkoritnigite identify bands which are attributable to phosphate and hydrogen phosphate anions proving some substitution of phosphate for arsenate in the structure of cobaltkoritnigite. The OH⋯O hydrogen bond lengths in the crystal structure of koritnigite were inferred from the Raman spectra and compared with those derived from the X-ray single crystal refinement. The presence of (AsO3OH)2− units in the crystal structure of cobaltkoritnigite and koritnigite was proved from the Raman spectra which supports the conclusions of the X-ray structure analysis.

Vibrational spectroscopic characterization of the sulphate-carbonate mineral burkeite: Implications for evaporites

Burkeite formation is important in saline evaporites and in pipe scales. Burkeite is an anhydrous sulphate-carbonate with an apparent variable anion ratio. Such a formula with two oxyanions lends itself to vibrational spectroscopy. Two symmetric sulphate stretching modes are observed, indicating at least at the molecular level the nonequivalence of the sulphate ions in the burkeite structure. The strong Raman band at 1065 cm−1 is assigned to the carbonate symmetric stretching vibration. The series of Raman bands at 622, 635, 645, and 704 cm−1 are assigned to the ν4 sulphate bending modes. The observation of multiple bands supports the concept of a reduction in symmetry of the sulphate anion from T d to C 3v or even C 2v.

A vibrational spectroscopic study of the silicate mineral kornerupine

We have studied the mineral kornerupine, a borosilicate mineral, by using a combination of scanning electron microscopy with energy-dispersive analysis and Raman and infrared spectroscopy. Qualitative chemical analysis of kornerupine shows a magnesium–aluminum silicate. Strong Raman bands at 925, 995, and 1051 cm−1 with bands of lesser intensity at 1035 and 1084 cm−1 are assigned to the silicon–oxygen stretching vibrations of the siloxane units. Raman bands at 923 and 947 cm−1 are attributed to the symmetrical stretching vibrations of trigonal boron. Infrared spectra show greater complexity and the infrared bands are more difficult to assign. Two intense Raman bands at 3547 and 3612 cm−1 are assigned to the stretching vibrations of hydroxyl units. The infrared bands are observed at 3544 and 3610 cm−1. Water is also identified in the spectra of kornerupine.

Vibrational spectroscopic study of poldervaartite CaCa[SiO3(OH)(OH)]

We have studied the mineral poldervaartite CaCa\[SiO3(OH)(OH)] which forms a series with its manganese analogue olmiite CaMn\[SiO3(OH)](OH) using a range of techniques including scanning electron microscopy, thermogravimetric analysis, Raman and infrared spectroscopy. Chemical analysis shows the mineral is reasonably pure and contains only calcium and manganese with low amounts of Al and F. Thermogravimetric analysis proves the mineral decomposes at 485 °C with a mass loss of 7.6% compared with the theoretical mass loss of 7.7%. A strong Raman band at 852 cm−1 is assigned to the SiO stretching vibration of the SiO3(OH) units. Two Raman bands at 914 and 953 cm−1 are attributed to the antisymmetric vibrations. Intense prominent peaks observed at 3487, 3502, 3509, 3521 and 3547 cm−1 are assigned to the OH stretching vibration of the SiO3(OH) units. The observation of multiple OH bands supports the concept of the non-equivalence of the OH units. Vibrational spectroscopy enables a detailed assessment of the molecular structure of poldervaartite.

A vibrational spectroscopic study of the silicate mineral normandite – NaCa(Mn2+,Fe2+)(Ti,Nb,Zr)Si2O7(O,F)2

We have studied the mineral normandite using a combination of scanning electron microscopy with energy dispersive spectroscopy and vibrational spectroscopy. The mineral normandite NaCa(Mn2+,Fe2+)(Ti,Nb,Zr)Si2O7(O,F)2 is a crystalline sodium calcium silicate which contains rare earth elements. Chemical analysis shows the mineral contains a range of elements including Na, Mn2+, Ca, Fe2+ and the rare earth element niobium. No Raman bands are observed above 1100 cm−1. The mineral is characterised by Raman bands observed at 724, 748, 782 and 813 cm−1. Infrared bands are broad; nevertheless bands may be resolved at 723, 860, 910, 958, 933, 1057 and 1073 cm−1. Intense Raman bands at 454, 477 and 513 cm−1 are attributed to OSiO bending modes. No Raman bands are observed in the hydroxyl stretching region, but low intensity infrared bands are observed at 3191 and 3450 cm−1. This observation brings into question the true formula of the mineral.

SEM, EDX and vibrational spectroscopic study of the phosphate mineral ushkovite MgFe3+2(PO4)2(OH)2·8H2O: Implications of the molecular structure

The mineral ushkovite has been analyzed using a combination of electron microscopy with EDX and vibrational spectroscopy. Chemical analysis shows the mineral contains P, Mg with very minor Fe. Thus, the formula of the studied ushkovite is Mg32+(PO4)2·8H2O. The Raman spectrum shows an intense band at 953 cm−1 assigned to the ν1 symmetric stretching mode. In the infrared spectra complexity exists with multiple antisymmetric stretching vibrations observed, due to the reduced tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong infrared bands around 827 cm−1 are attributed to water librational modes. The Raman spectra of the hydroxyl-stretching region are complex with overlapping broad bands. Hydroxyl stretching vibrations are identified at 2881, 2998, 3107, 3203, 3284 and 3457 cm−1. The wavenumber band at 3457 cm−1 is attributed to the presence of FeOH groups. This complexity is reflected in the water HOH bending modes where a strong infrared band centered around 1653 cm−1 is found. Such a band reflects the strong hydrogen bonding of the water molecules to the phosphate anions in adjacent layers. Spectra show three distinct OH bending bands from strongly hydrogen-bonded, weakly hydrogen bonded water and non-hydrogen bonded water. Vibrational spectroscopy enhances our knowledge of the molecular structure of ushkovite.

A SEM, EDS and vibrational spectroscopic study of the clay mineral fraipontite

The mineral fraipontite has been studied by using a combination of scanning electron microscopy with energy dispersive analysis and vibrational spectroscopy (infrared and Raman). Fraipontite is a member of the 1:1 clay minerals of the kaolinite-serpentine group. The mineral contains Zn and Cu and is of formula (Cu,Zn,Al)3(Si,Al)2O5(OH)4. Qualitative chemical analysis of fraipontite shows an aluminium silicate mineral with amounts of Cu and Zn. This kaolinite type mineral has been characterised by Raman and infrared spectroscopy; in this way aspects about the molecular structure of fraipontite clay are elucidated.

A vibrational spectroscopic study of the phosphate mineral vantasselite Al4(PO4)3(OH)3·9H2O

We have studied the phosphate mineral vantasselite Al4(PO4)3(OH)3·9H2O using a combination of SEM with EDX and Raman and infrared spectroscopy. Qualitative chemical analysis shows Al, Fe and P. Raman bands at 1013 and 1027cm−1 are assigned to the PO43−ν1 symmetric stretching mode. The observation of two bands suggests the non-equivalence of the phosphate units in the vantasselite structure. Raman bands at 1051, 1076 and 1090cm−1 are attributed to the PO43−ν3 antisymmetric stretching vibration. A comparison is made with the spectroscopy of wardite. Strong infrared bands at 1044, 1078, 1092, 1112, 1133, 1180 and 1210cm−1 are attributed to the PO43−ν3 antisymmetric stretching mode. Some of these bands may be due to δAl2OH deformation modes. Vibrational spectroscopy offers a mechanism for the study of the molecular structure of vantasselite.

A SEM, EDS and vibrational spectroscopic study of the tellurite mineral: Sonoraite Fe3+Te4+O3(OH)·H2O

We have undertaken a study of the tellurite mineral sonorite using electron microscopy with EDX combined with vibrational spectroscopy. Chemical analysis shows a homogeneous composition, with predominance of Te, Fe, Ce and In with minor amounts of S. Raman spectroscopy has been used to study the mineral sonoraite an examples of group A(XO3), with hydroxyl and water units in the mineral structure. The free tellurite ion has C3v symmetry and four modes, 2A1 and 2E. An intense Raman band at 734 cm−1 is assigned to the ν1 (TeO3)2− symmetric stretching mode. A band at 636 cm−1 is assigned to the ν3 (TeO3)2− antisymmetric stretching mode. Bands at 350 and 373 cm−1 and the two bands at 425 and 438 cm−1 are assigned to the (TeO3)2−ν2 (A1) bending mode and (TeO3)2−ν4 (E) bending modes. The sharp band at 3283 cm−1 assigned to the OH stretching vibration of the OH units is superimposed upon a broader spectral profile with Raman bands at 3215, 3302, 3349 and 3415 cm−1 are attributed to water stretching bands. The techniques of Raman and infrared spectroscopy are excellent for the study of tellurite minerals.

Resonance raman intensity analysis of polyatomic molecules

A time-dependent quantum mechanical (TDQM) method of wavepacket propagation in computing resonance Raman intensities for polyatomic systems, has been developed and demonstrated by applying it tocis-stilbene andtrans-azobenzene. In the case of the former, Raman excitation profiles (REPs) for the various vibrational modes have also been computed. It is observed that the calculated absorption spectrum and the REPs compare very well with the experimental results. A comparison of these results with those of the often semiclassical approach reveals that the TDQM method can be used to study polyatomic systems with as much ease as the semiclassical wavepacket method.