Structural characterization of the borate mineral inyoite – CaB3O3(OH)5⋅4(H2O)

We have studied the mineral Ca(H4B3O7)(OH)⋅4(H2O) or CaB3O3(OH)5⋅4(H2O) using electron microscopy and vibrational spectroscopy. The mineral has been characterized by a range of techniques including X-ray diffraction, thermal analysis, electron microscopy with EDX and vibrational spectroscopy. Electron microscopy shows a pure phase and the chemical analysis shows the presence of calcium only. The nominal resolution of the Raman spectrometer is of the order of 2 cm−1 and as such is sufficient enough to identify separate bands for the stretching bands of the two boron isotopes. Raman and infrared bands are assigned to the stretching and bending modes of trigonal and tetrahedral boron and the stretching modes of the hydroxyl and water units. By using a combination of techniques we have characterized the borate mineral inyoite.

A vibrational spectroscopic study of tengerite-(Y) Y2(CO3)3 2–3H2O

The mineral tengerite-(Y) has been studied by vibrational spectroscopy. Multiple carbonate stretching modes are observed and support the concept of non-equivalent carbonate units in the tengerite-(Y) structure. Intense sharp bands at 464, 479 and 508 cm−1 are assigned to YO stretching modes. Raman bands at 765 and 775 cm−1 are assigned to the CO32− ν4 bending modes and Raman bands at 589, 611, 674 and 689 cm−1 are assigned to the CO32− ν2 bending modes. Multiple Raman and infrared bands in the OH stretching region are observed, proving the existence of water in different molecular environments in the structure of tengerite-(Y).

The molecular structure of the borate mineral szaibelyite MgBO2(OH): A vibrational spectroscopic study

We have studied the borate mineral szaibelyite MgBO2(OH) using electron microscopy and vibrational spectroscopy. EDS spectra show a phase composed of Mg with minor amounts of Fe. Both tetrahedral and trigonal boron units are observed. The nominal resolution of the Raman spectrometer is of the order of 2 cm−1 and as such is sufficient enough to identify separate bands for the stretching bands of the two boron isotopes. The Raman band at 1099 cm−1 with a shoulder band at 1093 cm−1 is assigned to BO stretching vibration. Raman bands at 1144, 1157, 1229, 1318 cm−1 are attributed to the BOH in-plane bending modes. Raman bands at 836 and 988 cm−1 are attributed to the antisymmetric stretching modes of tetrahedral boron. The infrared bands at 3559 and 3547 cm−1 are assigned to hydroxyl stretching vibrations. Broad infrared bands at 3269 and 3398 cm−1 are assigned to water stretching vibrations. Infrared bands at 1306, 1352, 1391, 1437 cm−1 are assigned to the antisymmetric stretching vibrations of trigonal boron. Vibrational spectroscopy enables aspects of the molecular structure of the borate mineral szaibelyite to be assessed.

Raman and infrared spectroscopic characterization of the arsenate-bearing mineral tangdanite– and in comparison with the discredited mineral clinotyrolite

The minerals clinotyrolite and fuxiaotuite are discredited in terms of the mineral tangdanite. The mixed anion mineral tangdanite Ca2Cu9(AsO4)4(SO4)0.5(OH)9 9H2O has been studied using a combination of Raman and infrared spectroscopy. Characteristic bands associated with arsenate, sulphate and hydroxyl units are identified. Broad bands in the OH stretching region are observed and are resolved into component bands. These bands are assigned to water and hydroxyl stretching vibrations. Two intense Raman bands at 837 and approximately 734 cm−1 are assigned to the ν1 (AsO4)3− symmetric stretching and ν3 (AsO4)3− antisymmetric stretching modes. Infrared bands at 1023 cm−1 are assigned to the (SO4)2− ν1 symmetric stretching mode, and infrared bands at 1052, 1110 and 1132 cm−1 assigned to (SO4)2− ν3 antisymmetric stretching modes, confirming the presence of the sulphate anion in the tangdanite structure. Raman bands at 593 and 628 cm−1 are attributed to the (SO4)2− ν4 bending modes. Low-intensity Raman bands found at 457 and 472 cm−1 are assigned to the (AsO4)3− ν2 bending modes. A comparison is made with the previously obtained spectral data on the discredited mineral clinotyrolite.

SEM, EDX and Raman and infrared spectroscopic study of brianyoungite Zn3(CO3,SO4)(OH)4 from Esperanza Mine, Laurion District, Greece

The mineral brianyoungite, a carbonate–sulphate of zinc, has been studied by scanning electron microscopy (SEM) with chemical analysis using energy dispersive spectroscopy (EDX) and Raman and infrared spectroscopy. Multiple carbonate stretching modes are observed and support the concept of non-equivalent carbonate units in the brianyoungite structure. Intense Raman band at 1056 cm−1 with shoulder band at 1038 cm−1 is assigned to the CO32− ν1 symmetric stretching mode. Two intense Raman bands at 973 and 984 cm−1 are assigned to the symmetric stretching modes of the SO42− anion. The observation of two bands supports the concept of the non-equivalence of sulphate units in the brianyoungite structure. Raman bands at 704 and 736 cm−1 are assigned to the CO32− ν4 bending modes and Raman bands at 507, 528, 609 and 638 cm−1 are assigned to the CO32− ν2 bending modes. Multiple Raman and infrared bands in the OH stretching region are observed, proving the existence of water and hydroxyl units in different molecular environments in the structure of brianyoungite. Vibrational spectroscopy enhances our knowledge of the molecular structure of brianyoungite.

A Raman and infrared spectroscopic study of the sulphate mineral aluminite Al2(SO4)(OH)4·7H2O

The mineral aluminite has been studied using a number of techniques, including scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDX) and Raman and infrared spectroscopy. Raman spectroscopy identifies multiple sulphate symmetric stretching modes in line with the three sulphate crystallographically different sites. Raman spectroscopy also identifies a low intensity band at 1069 cm−1 which may be attributed to a carbonate symmetric stretching mode, indicating the presence of thaumasite. The observation of multiple bands in this ν4 spectral region offers evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 3588 cm−1 is assigned to the OH unit stretching vibration and the broad feature at around 3439 cm−1 to water stretching bands. Water stretching vibrations are observed at 3157, 3294, 3378 and 3439 cm−1. Vibrational spectroscopy enables an assessment of the molecular structure of aluminite to be made.

Scanning electron microscopy with energy dispersive spectroscopy and Raman and infrared spectroscopic study of tilleyite Ca5Si2O7(CO3)2-Y

The mineral tilleyite-Y, a carbonate-silicate of calcium, has been studied by scanning electron microscopy with chemical analysis using energy dispersive spectroscopy (EDX) and Raman and infrared spectroscopy. Multiple carbonate stretching modes are observed and support the concept of non-equivalent carbonate units in the tilleyite structure. Multiple Raman and infrared bands in the OH stretching region are observed, proving the existence of water in different molecular environments in the structure of tilleyite. Vibrational spectroscopy offers new information on the mineral tilleyite.

Raman and infrared spectroscopic study of the borate mineral kaliborite

We have studied the mineral kaliborite. The sample originated from the Inder B deposit, Atyrau Province, Kazakhstan, and is part of the collection of the Geology Department of the Federal University of Ouro Preto, Minas Gerais, Brazil. The mineral is characterized by a single intense Raman band at 756 cm−1 assigned to the symmetric stretching modes of trigonal boron. Raman bands at 1229 and 1309 cm−1 are assigned to hydroxyl in-plane bending modes of boron hydroxyl units. Raman bands are resolved at 2929, 3041, 3133, 3172, 3202, 3245, 3336, 3398, and 3517 cm−1. These Raman bands are assigned to water stretching vibrations. A very intense sharp Raman band at 3597 cm−1 with a shoulder band at 3590 cm−1 is assigned to the stretching vibration of the hydroxyl units. The Raman data are complimented with infrared data and compared with the spectrum of kaliborite downloaded from the Arizona State University database. Differences are noted between the spectrum obtained in this work and that from the Arizona State University database. This research shows that minerals stored in a museum mineral collection age with time. Vibrational spectroscopy enhances our knowledge of the molecular structure of kaliborite.

Infrared Spectra of Dimethylquinolines in the Gas Phase: Experiment and Theory

Infrared spectra of atmospherically important dimethylquinolines (DMQs), namely 2,4-DMQ, 2,6-DMQ, 2,7-DMQ, and 2,8-DMQ in the gas phase at 80 degrees C were recorded using a long variable path-length cell. DFT calculations were carried out to assign the bands in the experimentally observed spectra at the B3LYP/6-31G* level of theory. The spectral assignments particularly for the C-H stretching modes could not be made unambiguously using calculated anharmonic or scaled harmonic frequencies. To resolve this problem, a scaled force field method of assignment was used. Assignment of fundamental modes was confirmed by potential energy distributions (PEDs) of the normal modes derived by the scaled force fields using a modified version of the UMAT program in the QCPE package. We demonstrate that for large molecules such as the DMQs, the scaling of the force field is more effective in arriving at the correct assignment of the fundamentals for a quantitative vibrational analysis. An error analysis of the mean deviation of the calculated harmonic, anharmonic, and force field fitted frequencies from the observed frequency provides strong evidence for the correctness of the assignment.

Perturbation of the infrared spectrum of lanthanum cobaltate induced by vibronic coupling

Anomalous changes in the infrared intensity of the cobalt-oxygen stretching modes in the infrared spectrum of lanthanum cobaltate (LaCoO3) suggest vibronic coupling. This phenomenon has been studied by infrared vibrational spectroscopy both by temperature-induced changes of spin-state occupation and pressure-induced changes of the crystal field splitting 10Dq.

Conformation and orientation of alkyl chains in the layered organic-inorganic hybrids: (CnH2n+1NH3)(2)PbI4 (n=12,16,18)

Layered organic inorganic hybrids based on perovskite-derived alkylammonium lead halides have been demonstrated as important new materials in the construction of molecular electronic devices. Typical of this class of materials are the single-perovskite slab lead iodides of the general formula (CnH2n+1NH3)(2)PbI4. While for small n, these compounds are amenable to single-crystal structure determination, the increasing degree of disorder in the long chain (n = 12,14...) compounds makes such an analysis difficult. In this study, we use powder X-ray diffraction, and vibrational and C-13 NMR spectroscopies to establish the conformation, orientation and organization of hydrocarbon chains in the series of layered alkylammonium lead iodides (CnH2n+1NH3)(2)PbI4 (n = 12,16,18). We find that the alkyl chains adopt a tilted bilayer arrangement, while the structure of the inorganic layer remains invariant with respect to the value of n. Conformation-sensitive methylene stretching modes in the infrared and Raman spectra, as well as the C-13 NMR spectra indicate that bonds in the methylene chain are in trans configuration. The skeletal modes of the alkyl chain in the Raman spectra establish that there is a high degree of all-trans conformational registry for the values of n studied here. From the orientation dependence of the infrared spectra of crystals of (CnH2n+1NH3)(2)PbI4 ( n = 12,16), we find that the molecular axis of the all-trans alkyl chains are tilted away from the interlayer normal by an angle of 55degrees. This value of this tilt angle is consistent with the dependence of the c lattice expansion as a function of n, as determined from powder X-ray diffraction.

Microwave, infrared-microwave double resonance, and theoretical studies of C2H4 center dot center dot center dot H2S complex

In this manuscript, rotational spectra of four new isotopologues of the S-H center dot center dot center dot pi bonded C2H4 center dot center dot center dot H2S complex, i.e., C2D4 center dot center dot center dot H2S, C2D4 center dot center dot center dot D2S, C2D4 center dot center dot center dot HDS, and (CCH4)-C-13 center dot center dot center dot H2S have been reported and analyzed. All isotopologues except C2D4 center dot center dot center dot HDS show a four line pattern whereas a doubling of the transition frequencies was observed for C2D4 center dot center dot center dot HDS. These results together with our previous report on the title complex M. Goswami, P. K. Mandal, D. J. Ramdass, and E. Arunan, Chem. Phys. Lett. 393(1-3), 22-27 (2004)] confirm that both subunits (C2H4 and H2S) are involved in large amplitude motions leading to a splitting of each rotational transition to a quartet. Further, the results also confirm that the motions which are responsible for the observed splittings involve both monomers. Molecular symmetry group analysis, considering the interchange of equivalent H atoms in H2S and C2H4 could explain the observed four line pattern and their intensities in the microwave spectrum. In addition, hydride stretching fundamentals of the complex were measured using coherence-converted population transfer Fourier Transform Microwave-infrared (IR-MW double resonance) experiments in the S-H and C-H stretch regions. Changes in the tunneling splittings upon vibrational excitation are consistent with the isotopic dependence of pure rotational transitions. A complexation shift of 2.7-6.5 cm(-1) has been observed in the two fundamental S-H stretching modes of the H2S monomer in the complex. Vibrational pre-dissociation in the bound S-H stretch has been detected whereas the instrument-limited line-shapes in other S-H and C-H stretches indicate slower pre-dissociation rate. Some local perturbations in the vibrational spectra have been observed. Two combination bands have been observed corresponding to both the S-H stretching fundamentals and what appears to be the intermolecular stretching mode at 55 cm(-1). The tunneling splitting involved in the rotation of C2H4 unit has been deduced to be 1.5 GHz from the IR-MW results. In addition, ab initio barrier heights derived for different motions of the monomers support the experimental results and provide further insight into the motions causing the splitting. (C) 2013 AIP Publishing LLC.

Fe as Hydrogen/Halogen Bond Acceptor in Square Pyramidal Fe(CO)(5)

Hydrogen bonded complexes formed between the square pyramidal Fe(CO)(5) with HX (X = F, Cl, Br), showing X-H center dot center dot center dot Fe interactions, have been investigated theoretically using density functional theory (DFT) including dispersion correction. Geometry, interaction energy, and large red shift of about 400 cm(-1) in the FIX stretching frequency confirm X-H center dot center dot center dot Fe hydrogen bond formation. In the (CO)(5)Fe center dot center dot center dot HBr complex, following the significant red shift, the HBr stretching mode is coupled with the carbonyl stretching modes. This clearly affects the correlation between frequency shift and binding energy, which is a hallmark of hydrogen bonds. Atoms in Molecule (AIM) theoretical analyses show the presence of a bond critical point between the iron and the hydrogen of FIX and significant mutual penetration. These X-H center dot center dot center dot Fe hydrogen bonds follow most but not all of the eight criteria proposed by Koch and Popelier (J. Phys. Chem. 1995, 99, 9747) based on their investigations on C-H center dot center dot center dot O hydrogen bonds. Natural bond orbital (NBO) analysis indicates charge transfer from the organometallic system to the hydrogen bond donor. However, there is no correlation between the extent of charge transfer and interaction,energy, contrary to what is proposed in the recent IUPAC recommendation (Pure Appl.. Chem. 2011, 83, 1637). The ``hydrogen bond radius'' for iron has been determined to be 1.60 +/- 0.02 angstrom, and not surprisingly it is between the covalent (127 angstrom) and van der Waals (2.0) radii of Fe. DFT and AIM theoretical studies reveal that Fe in square pyramidal Fe(CO)(5) can also form halogen bond with CIF and ClH as ``halogen bond donor''. Both these complexes show mutual penetration as well, though the Fe center dot center dot center dot Cl distance is closer to the sum of van der Waals radii of Fe and Cl in (CO)5Fe center dot center dot center dot ClH, and it is about 1 angstrom less in (CO)(5)Fe center dot center dot center dot ClF.

Raman spectroscopic investigation of pure and ytterbium-doped rare earth silicate crystals

Raman spectroscopy was used to study the molecular structure of a series of selected rare earth (RE) silicate crystals including Y2SiO5 (YSO), LU2SiO5 (LSO), (Lu0.5Y0.5)(2)SiO5 (LYSO) and their ytterbium-doped samples. Raman spectra show resolved bands below 500 cm(-1) region assigned to the modes of SiO4 and oxygen vibrations. Multiple bands indicate the nonequivalence of the RE-O bonds and the lifting of the degeneracy of the RE ion vibration. Low intensity bands below 500 cm(-1) are an indication of impurities. The (SiO4)(4-) tetrahedra are characterized by bands near 200 cm(-1) which show a separation of the components of nu(4) and nu(2), in the 500-700 cm(-1) region which are attributed to the distorting bending vibration and in the 880-1000 cm(-1) region which are attributed to the symmetric and antisymmetric stretching vibrational modes. The majority of the bands in the 300-610 cm(-1) region of Re2SiO5 were found to arise from vibrations involving both Si and RE ions, indicating that there is considerable mixing of Si displacements with Si-O bending modes and RE-0 stretching modes. The Raman spectra of RE silicate crystals were analyzed in terms of the molecular structure of the crystals, which enabled separation of the bands attributed to distinct vibrational units. Copyright (C) 2007 John Wiley & Sons, Ltd.

Vibrational spectroscopic studies of the structure of di-amino acid peptides. Part II: cyclo(L-Asp-L-Asp) in the solid state and in aqueous solution

Solid-state protonated and N,O-deuterated Fourier transform infrared (IR) and Raman scattering spectra together with the protonated and deuterated Raman spectra in aqueous solution of the cyclic di-amino acid peptide cyclo(L-Asp-L-Asp) are reported. Vibrational band assignments have been made on the basis of comparisons with previously cited literature values for diketopiperazine (DKP) derivatives and normal coordinate analyses for both the protonated and deuterated species based upon DFT calculations at the B3-LYP/cc-pVDZ level of the isolated molecule in the gas phase. The calculated minimum energy structure for cyclo(L-Asp-L-Asp), assuming C-2 symmetry, predicts a boat conformation for the DKP ring with both the two L-aspartyl side chains being folded slightly above the ring. The C=O stretching vibrations have been assigned for the side-chain carboxylic acid group (e.g. at 1693 and 1670 cm(-1) in the Raman spectrum) and the cis amide I bands (e.g. at 1660 cm(-1) in the Raman spectrum). The presence of two bands for the carboxylic acid C=O stretching modes in the solid-state Raman spectrum can be accounted for by factor group splitting of the two nonequivalent molecules in a crystallographic unit cell. The cis amide II band is observed at 1489 cm(-1) in the solid-state Raman spectrum, which is in agreement with results for cyclic di-amino acid peptide molecules examined previously in the solid state, where the DKP ring adopts a boat conformation. Additionally, it also appears that as the molecular mass of the substituent on the C-alpha atom is increased, the amide II band wavenumber decreases to below 1500 cm(-1); this may be a consequence of increased strain on the DKP ring. The cis amide II Raman band is characterized by its relatively small deuterium shift (29 cm(-1)), which indicates that this band has a smaller N-H bending contribution than the trans amide II vibrational band observed for linear peptides.