Lattice Vibration Spectra. XX. Infrared and Raman Spectra of BaCl2•2H2O and BaCl2•2D2O

Lutz, H. D.; Pobitschka, W.; Frischemeier, B.; Becker, Robert A.

doi:10.1366/000370278774330847

Cited by 21 publications

(9 citation statements)

References 12 publications

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“…The latter is usually referred to as the association band [60] because of its original assignment to the transition (v2 + vL -vT). More recent work on solid water in crystalline hydrates [61] would indicate that v2 + vR (R, librational modes) may be preferred. A summary of the bands involved is given in table 1.…”

Section: Resultsmentioning

confidence: 99%

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Infrared and far-infrared spectroscopic studies on the structure of water in lyotropic liquid crystals

1987

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Studies on the infrared and far-infrared spectra of water in lyotropic liquidcrystalline phases of dodecyltrimethyl ammonium chloride (and related materials) have shown the existence of at least two severely perturbed types of water molecule -both very different from bulk water. Band shifts, half-widths and relative intensities change rapidly over the concentration range, but show no discontinuities at phase boundaries (including the gel/lamellar boundary). The water molecules therefore probe only the short-range interactions between head group and counterion and do not reflect changes in long-range micellar interactions in the different mesophases. These data support the equilibrium binding model for water-surfactant interactions at polar organic interfaces and tend to refute the existence of different polarized layers. As such, they may eventually help to cast light on the nature of hydration forces between the bilayers in lamellar phases. IntroductionThe binding of water at polar charged organic interfaces has been a topic of considerable interest among surface chemists, spectroscopists and biochemists (and biophysicists) for the past 20 years. The state or structure of water in ordered phases (micelles, mesophases, microemulsions) has been perceived to be important: for example, for the stabilization of the bilayer structures (lamellar phases) from which biomembranes are formed [l-111 and for the adhesion [8] and fusion [7] of such membranes. Accordingly, there have been a range of spectroscopic measurements aimed at distinguishing biological (i.e. perturbed or bound) water from bulk water. The most extensive studies have been made using N.M.R. techniques, notably *H and "0 quadrupolar splitting [12-221 and 'H, 'H, "0 nuclear relaxation times [15][16][17][18]. These have been employed to monitor the ordering and motional freedom of the water molecules at organic interfaces, through the well-known order and relaxation parameters [I 8, 191. However, there have also been microwave (dielectric) [3 1-35], far-infrared [3&38], mid-infrared [39-541 and Raman [55] spectroscopic measurements aimed at finding structural and motional changes caused by water molecules interacting at either.head group or counterion (or both). It is clear from the literature that the interpretation of such spectra is far from straightforward or conclusive and often different models will apparently fit the same data. Certainly, a consensus of opinion on the crucial question as to whether water molecules in mesophases form perturbed and distinct layers [lo, 111, or whether there is simply an equilibrium

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Section: Resultsmentioning

confidence: 99%

“…However, some of these shoulders do become evident at much lower concentrations of surfactant and are, in all probability due to the perturbation of water molecules due to cation or anion binding[61,62].…”

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confidence: 99%

Infrared and far-infrared spectroscopic studies on the structure of water in lyotropic liquid crystals

1987

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“…[30] Jain et al [31] proposed that the wavenumbers of the rocking, twisting and wagging vibrations should follow the sequence ρ > τ > ω, whereas Makitova et al [7] suggested the order ρ > ω > τ. The assignment made by Lutz et al [25] located the wagging, twisting and rocking vibrations in 610-725, 490-570 and 410-545 cm −1 regions, respectively. These results were based on the deuteration of the studied materials.…”

Section: Raman Spectramentioning

confidence: 97%

“…[21 -24] Static and dynamic models of the interactions between the water molecules in the unit cell have been considered. [25,26] The librational modes of the water units have been found in the regions 660-780 and 340-430 cm −1 , both in the IR and Raman spectra. [27 -29] The assignment of other external vibrations of the water units in the hydrates is not consistent.…”

Section: Raman Spectramentioning

confidence: 99%

Polarised IR and Raman spectra of non‐centrosymmetric Na₃Li(MoO₄)₂· 6H₂O crystal—a new Raman laser material

Hanuza

Mączka

Lorenc

et al. 2009

J Raman Spectroscopy

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Polarised IR and Raman spectra of Na 3 Li(MoO 4 ) 2 · 6H 2 O single crystal were measured. Discussion of the results is based on the factor group approach for the trigonal R 3c(C 3v 6 ) space group with Z = 2. The assignment of the observed bands was performed on the basis of their polarisation behaviour and literature data. The obtained results for the spontaneous Raman scattering were used in the analysis of the stimulated Raman spectra of the material studied -a new Raman laser crystal. The promoting modes of the stimulated effect were identified.

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“…This splitting is caused by the possibility of different structural arrangement of the H and D atoms in salt hydrates with asymmetric water molecules' and was first found in the spectra of BaC12.2H20. 3 The H D O librational fundamentals can be observed as sharp distinct bands only in isotopically dilute samples, if overlap with other bands is absent. In samples with higher content of H D O molecules, broadening and additional splittings of the H D O librations, not fully resolved in the spectra, take place caused by dynamic coupling of the vibrations.…”

Section: Librational Modes Of the Water Moleculesmentioning

confidence: 99%

Lattice vibration spectra. XXII—infrared and Raman spectra of strontium chloride dihydrate, SrCl₂·2H₂O and SrCl₂·2(H, D)₂O

Lutz

Pobitschka

Christian

et al. 1979

J Raman Spectroscopy

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~ ~~The infrared absorption and Raman spectra of SrClz-2H20 powder as well as SrClZ.2Dz0, and partially deuterated and isotopically dilute samples, have been recorded in the range from 30 to 4000 cm-' at 95 and 295 K and analysed with regard to the strongly asymmetric force field in the H 2 0 molecules. This is shown by an unusually large splitting of the OH and OD stretching fundamentals of the HDO molecules: 3426 and 3243 cm-' and 2534 and 2408 cm-' respectively at 95 K. Uncoupled OD stretching frequencies of SrC12.6H20 and SrCI,-HzO are also presented. In SrClz.2H20 both a relatively strong and a weak hydrogen bond to chloride ions are present; these are essentially straight. The spectra of SrCIz-2Hz0 exhibit the following characteristics: (1) no intramolecular coupling of the OH stretching vibrations; (2) very large Fermi resonance of vOH and 2 & 4 (3) the same high intensity of HzO twisting librations in the infrared spectra as for wagging and rocking modes; (4) splitting of the librational fundamentals of the HDO molecules, as large as 100 cm-', caused by different structural arrangements of the H and D atoms in the asymmetric HzO molecules; and (5) strong intermolecular coupling of bending and librational fundamentals, which results in correlation splittings up to 75 cm-'. Possibilities of assigning the librational modes of HzO molecules which are in an asymmetric force field are discussed.

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Lattice Vibration Spectra. XX. Infrared and Raman Spectra of BaCl₂•2H₂O and BaCl₂•2D₂O

Cited by 21 publications

References 12 publications

Infrared and far-infrared spectroscopic studies on the structure of water in lyotropic liquid crystals

Infrared and far-infrared spectroscopic studies on the structure of water in lyotropic liquid crystals

Polarised IR and Raman spectra of non‐centrosymmetric Na₃Li(MoO₄)₂· 6H₂O crystal—a new Raman laser material

Lattice vibration spectra. XXII—infrared and Raman spectra of strontium chloride dihydrate, SrCl₂·2H₂O and SrCl₂·2(H, D)₂O

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Lattice Vibration Spectra. XX. Infrared and Raman Spectra of BaCl2•2H2O and BaCl2•2D2O

Cited by 21 publications

References 12 publications

Infrared and far-infrared spectroscopic studies on the structure of water in lyotropic liquid crystals

Infrared and far-infrared spectroscopic studies on the structure of water in lyotropic liquid crystals

Polarised IR and Raman spectra of non‐centrosymmetric Na3Li(MoO4)2· 6H2O crystal—a new Raman laser material

Lattice vibration spectra. XXII—infrared and Raman spectra of strontium chloride dihydrate, SrCl2·2H2O and SrCl2·2(H, D)2O

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Product

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Lattice Vibration Spectra. XX. Infrared and Raman Spectra of BaCl₂•2H₂O and BaCl₂•2D₂O

Polarised IR and Raman spectra of non‐centrosymmetric Na₃Li(MoO₄)₂· 6H₂O crystal—a new Raman laser material

Lattice vibration spectra. XXII—infrared and Raman spectra of strontium chloride dihydrate, SrCl₂·2H₂O and SrCl₂·2(H, D)₂O