Raman spectroscopy of likasite at 298 and 77 K

Raman spectroscopy at 298 and 77K has been used to study the structure of likasite, a naturally occurring basic copper(II) nitrate of formula Cu3NO3(OH)5.2H2O. An intense sharp band is observed at 3522 cm(-1) at 298 K which splits into two bands at 3522 and 3505 cm(-1) at 77 K and is assigned to the OH stretching mode. The two OH stretching bands at 3522 and 3505 provide estimates of the hydrogen bond distances of these units as 2.9315 and 2.9028 angstroms. The significance of this result is that equivalent OH units in the 298 K spectrum become two non-equivalent OH units at 77 K suggesting a structural change by cooling to liquid nitrogen temperature. A number of broad bands are observed in the 298 K spectrum at 3452, 3338, 3281 and 3040 cm(-1) assigned to H2O stretching vibrations with estimates of the hydrogen bond distances of 2.8231, 2.7639, 2.7358 and 2.6436 angstroms. Three sharp bands are observed at 77 K at 1052, 1050 and 1048 cm(-1) attributed to the nu1 symmetric stretching mode of the NO3 units. Only a single band at 1050 cm(-1) is observed at 298 K, suggesting the non-equivalence of the NO3 units at 77 K, confirming structural changes in likasite by cooling to 77 K.     

Raman spectroscopy of urea and urea-intercalated kaolinites at 77 K

The Raman spectra of urea and urea-intercalated kaolinites have been recorded at 77 K using a Renishaw Raman microprobe equipped with liquid nitrogen cooled microscope stage. The NH2 stretching modes of urea were observed as four bands at 3250, 3321, 3355 and 3425 cm(-1) at 77 K. These four bands are attributed to a change in conformation upon cooling to liquid nitrogen temperature. Upon intercalation of urea into both low and high defect kaolinites, only two bands were observed near 3390 and 3410 cm(-1). This is explained by hydrogen bonding between the amine groups of urea and oxygen atoms of the siloxane layer of kaolinite with only one urea conformation. When the intercalated low defect kaolinite was cooled to 77 K, the bands near 3700 cm(-1) attributed to the stretching modes of the inner surface hydroxyls disappeared and a new band was observed at 3615 cm(-1). This is explained by the breaking of hydrogen bonds involving OH groups of the gibbsite-like layer and formation of new bonds to the C=O group of the intercalated urea. Thus it is suggested that at low temperatures two kinds of hydrogen bonds are formed by urea molecules in urea-intercalated kaolinite.     

Towards a single crystal Raman spectrum of kaolinite at 77 K

The Raman spectra at 77 K of the hydroxyl stretching of kaolinite were obtained along the three axes perpendicular to the crystal faces. Raman bands were observed at 3616, 3658 and 3677 cm(-1) together with a distinct band observed at 3691 cm(-1) and a broad profile between 3695 and 3715 cm(-1). The band at 3616 cm(-1) is assigned to the inner hydroxyl. The bands at 3658 and 3677 cm(-1) are attributed to the out-of-phase vibrations of the inner surface hydroxyls. The Raman spectra of the in-phase vibrations of the inner-surface hydroxyl-stretching region are described in terms of transverse and longitudinal optic splitting. The band at 3691 cm(-1) is assigned to the transverse optic and the broad profile to the longitudinal optic mode. This splitting remained even at liquid nitrogen temperature. The transverse optic vibration may be curve resolved into two or three bands, which are attributed to different types of hydroxyl groups in the kaolinite.     

Radiation products at 77 K in trehalose single crystals: EMR and DFT analysis

The radicals obtained in trehalose dihydrate single crystals after 77 K X-irradiation have been investigated at the same temperature using X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and ENDOR-induced EPR (EIE) techniques. Five proton hyperfine coupling tensors were unambiguously determined from the ENDOR measurements and assigned to three carbon-centered radical species (T1, T1*, and T2) based on the EIE spectra. EPR angular variations revealed the presence of four additional alkoxy radical species (T3 to T6) and allowed determination of their g tensors. Using periodic density functional theory (DFT) calculations, T1/T1*, T2, and T3 were identified as H-loss species centered at C4, C1', and O2', respectively. The T4 radical is proposed to have the unpaired electron at O4, but considerable discrepancies between experimental and calculated HFC values indicate it is not simply the (net) H-loss species. No suitable models were found for T5 and T6. These exhibit a markedly larger g anisotropy than T3 and T4, which were not reproduced by any of our DFT calculations.     

Photoinduced oxygen adsorption of AgBr crystals at 77 K

Photoinduced adsorption (PIA) of oxygen molecules on AgBr films at 77 K has been experimentally observed and investigated. Lifetimes of PIA centers and desorption activation energies of O₂ molecules have been determined. The process is suggested to compete with the ionic step of AgBr photolysis.

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- () - AgBr 77 K. - O₂. , , - AgBr.

     

The direct observation of hydrogen molecules in irradiated solid ethanol by means of Raman spectroscopy at 77 K

Hydrogen molecules produced in ethanol glass and crystal which were irradiated at 77 K were detected directly by Raman spectroscopy at 77 K. The bands at 4133 cm^-1 for ethanol glass and 4155 cm^-1 for ethanol crystal were ascribed to the stretching vibration of hydrogen molecules. The assignment of the bands was confirmed by spectra of irradiated ethanol-d₁ and -d₅ glasses: a new band observed at 3610 cm^-1 was due to the vibration of HD molecules. The intensity of the band at 4133 cm^-1 decreased in irradiated ethanol glass containing the electron scavenger, CCl₄, at 77 K. This presents further evidence that the 4133 cm^-1 band is due to hydrogen molecules, since the solvated electron is a precursor of the hydrogen atom.     

Difference in the dynamic properties of chiral and racemic crystals of serine studied by Raman spectroscopy at 3-295 K

Single-crystal polarized Raman spectra (60-4000 cm(-1) at 3 < or = T < or = 295 K) were measured for chiral L- and racemic DL-serine, alpha-amino-beta-hydroxypropionic acid, (NH3)+CH(CH2OH)(COO)-. The Raman spectra of dl-serine do not show any striking changes with temperature or on storage. In contrast to that, the dynamical properties of L-serine change at about 140 K. These changes can be interpreted as the reorientation of the side chain -CH2OH fragments of the zwitterions with respect to the backbone C-C bonds, resulting in the positional disorder of the O-H...O intermolecular H-bonds. The redistribution in the intensities of the Raman spectra of the crystals of L-serine stored for a long time (about a year) indicates the changes in the orientation of the molecular fragments in the direction normal to the axes of the head-to-tail chains. The difference in the thermodynamic functions of L- and DL-serine reported previously [Drebushchak, V. A.; Kovalevskaya, Yu. A.; Paukov, I. E.; Boldyreva, E. V. J. Therm. Anal. Calorim. 2007, 89 (2), 649-654] is explained by the difference in the spectra of external vibrations of the crystals.     

Raman spectra of deuteriated taurine single crystals

The polarized Raman spectra of partially deuteriated taurine [(ND3+)0.65(NH3+)0.35(CH2)2SO3-] crystals from x(zz)x and x(zy)x scattering geometries of the Ag and Bg irreducible representations of the factor group C2h are reported. The temperature-dependent Raman spectra of partially deuteriated taurine do not reveal any evidence of the structural phase transition undergone by normal taurine at about 250 K, but an anomaly observed in the 180 cm-1 band at approximately 120 K implies a different dynamic for this band (which is involved in a pressure-induced phase transition) in the deuteriated crystal.     

Single site electronic spectroscopy of free base octaethylporphyrin, octaethychlorin and their diacids in n-octane at 298K and 7K

Single site fluorescence and absorption spectra of free base octaethylporphyrin, octaethylchlorin and their respective diacids in n-octane at 298 K and 7 K are reported. Vibrational frequencies associated with the ground and excited states were determined from the spectra. All of these moieties exhibit well defined and narrow spectral features, with the exception of the octaethylchlorin diacid; it gives broad spectral bands even at 7 K. Respective Q and B origins were also identified.     

High pressure Raman spectroscopy of single crystals of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX)

To gain insight into the high-pressure polymorphism of RDX, an energetic crystal, Raman spectroscopy results were obtained for hydrostatic (up to 15 GPa) and non-hydrostatic (up to 22 GPa) compressions. Several distinct changes in the spectra were found at 4.0 +/- 0.3 GPa, confirming the alpha-gamma phase transition previously observed in polycrystalline samples. Detailed analyses of pressure-induced changes in the internal and external (lattice) modes revealed several features above 4 GPa: (i) splitting of both the A' and A' ' internal modes, (ii) a significant increase in the pressure dependence of the Raman shift for NO2 modes, and (iii) no apparent change in the number of external modes. It is proposed that the alpha-gamma phase transition leads to a rearrangement between the RDX molecules, which in turn significantly changes the intermolecular interaction experienced by the N-O bonds. Symmetry correlation analyses indicate that the gamma-polymorph may assume one of the three orthorhombic structures: D2h, C2v, or D2. On the basis of the available X-ray data, the D2h factor group is favored over the other structures, and it is proposed that gamma-phase RDX has a space group isomorphous with a point group D2h with eight molecules occupying the C1 symmetry sites, similar to the alpha-phase. It is believed that the factor group splitting can account for the observed increase in the number of modes in the gamma-phase. Spatial mapping of Raman modes in a non-hydrostatically compressed crystal up to 22 GPa revealed a large difference in mode position indicating a pressure gradient across the crystal. No apparent irreversible changes in the Raman spectra were observed under non-hydrostatic compression.     

On-line identification of trans- and cis-resveratrol by nonaqueous capillary electrophoresis/fluorescence spectroscopy at 77 K

This work presents a novel method for the accurate determining trans- and cis-resveratrol (3,5,4'-trihydroxystilbene) by nonaqueous capillary electrophoresis/fluorescence spectroscopy at 77 K. The proposed method permits not only the separation of resveratrol isomers, but also ensures that on-line spectra are readily distinguishable and unambiguously assigned. The experimental results also indicate that the effect of nonaqueous capillary electrophoresis buffer and low-temperature technique increase the detection limit by more than 150-fold.     

An algorithm to identify the existence and reproducibly obtain single crystals of salts and mixed crystals of amino acids suitable for single crystal XRD and Raman spectroscopy experiments

An algorithm is proposed to reproducibly obtain single crystals of salts and mixed crystals of amino acids with dicarboxylic acids and other small organic molecules. The resulting crystals are of high quality and have good faceting, which makes them suitable for single crystal XRD and Raman spectroscopic (including polarized radiation) experiments. The ease of the implementation and the possibility to reproduce the crystallization using equipment and materials that are available at virtually every laboratory are the hallmarks of the proposed algorithm, which involves two stages of work. During the first stage, the original components are screened, quickly and easily, to find new phases. The aim of the second stage is to obtain single crystals that meet the requirements of different research methods. An ideal case is the one whereby it is possible to control the size of well-faceted spaced apart crystals that grow within a few hours and are easy to separate from the surface.     

A classification of metaborate crystals based on Raman spectroscopy

The Raman spectra of crystals built solely of metaborate triangles provide fingerprint identification of three distinct network types. Classified according to increasing cation field strength these are: rings with degenerate intra-annular bonds and D_3h symmetry, distorted rings with alternating intra-annular bonds and C_3h symmetry, as well as chains. The occurrence of each network type has been associated with a characteristic range of cationic field strength. This approach led to the discovery of a hitherto unknown C_3h ring strontium metaborate crystal, with Sr²⁺ cations in 9- or 10-fold coordination to oxygen atoms. The Raman spectra of the mixed cation metaborates Ba₂Ca(B₂O₄)₃ and Ba₂Mg(B₂O₄)₃ confirm their C_3h-ring structure and clearly point to the fact that the synergetic effect of dissimilar cations to the metaborate network cannot be predicted by the additivity of their field strengths.     

Temperature-dependent Raman spectroscopy studies of phase transformations in the K2WO4 and the MgMoO4 crystals

Temperature-dependent Raman spectroscopy studies of K₂WO₄ and MgMoO₄ polycrystals were performed in order to obtain information about vibrational and structural changes in these materials as a function of temperature. The stability of the monoclinic phase for both K₂WO₄ and MgMoO₄ samples was assessed and our results indicated that this phase is stable in the 295–723 K and 300–770 K ranges for K₂WO₄ and MgMoO₄, respectively. It was observed that both samples underwent two phase transformations above room temperature. The first phase transformations which occur at about 633 K and 640 K for K₂WO₄ and MgMoO₄, respectively, is most likely connected with weak tilting and/or rotations of WO₄/MoO₄ tetrahedral units that lead to a disorder in the oxygen sublattice. Raman spectroscopy data also indicated that K₂WO₄ and MgMoO₄ exhibited a first-order phase transition at around 723 K and 770 K, respectively, changing from monoclinic to hexagonal symmetry.     

High-resolution spectroscopy of bacteriochlorin in n-alkane host crystals at 4.2 K

Site-selection spectroscopy of free-base bacteriochlorin (7,8,17,18-tetrahydroporphin) in n-hexane, n-octane and n-decane at 4.2 K are reported. The vibrational frequencies of the ground state, and first and second excited singlet states were determined from the fluorescence and excitation spectra. Low-frequency modes were observed, from which the angle of reorientation of the Molecule upon excitation is estimated (< 1.5°).     

Solubility of Elemental Sulfur in Water at 298 K

Abstract

The solubility of elemental rhombic sulfur in water is 1.9(±0.6) × 10^?8 mole S₈·kg^?1. This value is in agreement with thermodynamic considerations on the solubility of sulfur and experimental data on sulfur hydrosols.     

Infrared and Raman spectroscopy at high pressures

Pressure is accepted theoretically as a useful variable. However in a studies on liquid or solid samples, it is still relatively unusual for pressure to be used as an experimental variable. The reluctance of experimentalists to use this theoretically attractive variable is caused mainly by the technical difficulties associated with the use of sufficiently high pressures. In this talk I will try to show that in many cases the experimental limitations are no longer those introduced by the use of high pressures. High pressure spectroscopic studies clearly imply the use of high pressure spectroscopic cells. A brief account will therefore be given of the various types of high pressure optical cells which are currently being used for spectroscopic studies. Each individual high pressure spectroscopic study has its own special justification. However there are a few quite general observations that can be made which cover many of the specific objectives of individual high pressure spectroscopic studies. For example:(i) pressure induced frequency shifts carry unambiguous information about anharmonic terms in the relevant potential function (i.e. the potential V is a function of distance d. therefore pressure can be used to change d and study V.)(ii) all known materials undergo structural phase transitions if the form which is thermodynamically stable under ambient conditions is compressed to high enough pressures: these high pressure phases should be studied.(iii) as the application of pressure forces a material towards a phase transition, the spectroscopic study can be used to gain information about the approaching structural instability.(iv) virtually all infrared and Raman spectra contain examples of Fermi resonance which confuse the interpretation of the spectra and the effects of pressure are valuable aids to the correct assignment of the resonating levels.(v) pressure induced frequency shifts can often give extra information to help with the more reliable assignment of features within a spectrum.The above points will be discussed and illustrated by examples chosen mainly from recent work by members of the spectroscopy group at King's College London.