Raman spectroscopy structure

Figure 1.15. O2 adducts of (A) the heme/Cu site of HCOs (compound A) and (B and C) two heme/Cu analogs . Structure A is derived from resonance Raman spectroscopy, structure B (derived from 2cFeCu, Figure 1.14, Table 1.2) is based on resonance Raman and H NMR spectroscopic data and structure C is determined by single-crystal X-ray analysis counterion (BPh ) is omitted for clarity . Replication of both the distal and proximal environment in 2cFeCu was required to obtain the biologically relevant ferric-superoxide/Cu isomer of the O2 adduct, not the more common ferric-peroxo-Cu isomer.

Myers A B and Mathies R A 1987 Resonance Raman intensities A probe of excited-state structure and dynamics Biological Applications of Raman Spectroscopy yo 2, ed T G Spiro (New York Wiley-Interscience) pp 1-58... 

Vibrational spectroscopy provides detailed infonnation on both structure and dynamics of molecular species. Infrared (IR) and Raman spectroscopy are the most connnonly used methods, and will be covered in detail in this chapter. There exist other methods to obtain vibrational spectra, but those are somewhat more specialized and used less often. They are discussed in other chapters, and include inelastic neutron scattering (INS), helium atom scattering, electron energy loss spectroscopy (EELS), photoelectron spectroscopy, among others. 

Kincaid J R 1995 Structure and dynamics of transient species using time-resolved resonance Raman-spectroscopy Biochemical Spectroscopy Methods Enzymol. vol 246, ed K Sauer (San Diego, CA Academic) pp 460-501... 

In order to develop the theoretical structure that underlies each of the many Raman spectroscopies at third... 

Asher S A, Chi Z, Holtz J S W, Lednev I K, Karnoup A S and Sparrow M C 1998 UV resonance Raman studies of protein structure and dynamics XWf/r int. Conf on Raman Spectroscopy ed A M Heyns (New York Wley) pp 11-14... 

Barron L D, Hecht L, Bell A F and WIson G 1996 Raman optical activity an incisive probe of chirality and biomolecular structure and dynamics ICORS 96 XVth Int. Conf. on Raman Spectroscopy ed S A Asher and P B Stein (New York Wley) pp 1212-15... 

Figure Bl.22.6. Raman spectra in the C-H stretching region from 2-butanol (left frame) and 2-butanethiol (right), each either as bulk liquid (top traces) or adsorbed on a rough silver electrode surface (bottom). An analysis of the relative intensities of the different vibrational modes led to tire proposed adsorption structures depicted in the corresponding panels [53], This example illustrates the usefiilness of Raman spectroscopy for the detennination of adsorption geometries, but also points to its main limitation, namely the need to use rough silver surfaces to achieve adequate signal-to-noise levels.

Friedman J M 1994 Time-resolved resonance Raman spectroscopy as probe of structure, dynamics, and reactivity in hemoglobin Methods Enzymol. 232 205-31... 

The vibrational states of a molecule are observed experimentally via infrared and Raman spectroscopy. These techniques can help to determine molecular structure and environment. In order to gain such useful information, it is necessary to determine what vibrational motion corresponds to each peak in the spectrum. This assignment can be quite difficult due to the large number of closely spaced peaks possible even in fairly simple molecules. In order to aid in this assignment, many workers use computer simulations to calculate the vibrational frequencies of molecules. This chapter presents a brief description of the various computational techniques available. 

The planar structure of thiazole (159) implies for the molecule a Cj-type symmetry (Fig. 1-8) and means that all the 18 fundamental vibrations are active in infrared and in Raman spectroscopy. Table 1-22 lists the predictions made on the basis of this symmetry for thiazole. 

Raman spectroscopy is primarily a structural characterization tool. The spectrum is more sensitive to the lengths, streng ths, and arrangement of bonds in a material than it is to the chemical composition. The Raman spectmm of crystals likewise responds more to details of defects and disorder than to trace impurities and related chemical imperfections. 

Raman spectroscopy is sensitive to ordering arrangements of crystal structures, the effect depending on the type of order. Ordering atoms onto specific lattice sites in... 

Raman spectroscopy is particularly useful for investigating the structure of noncrystalline solids. The vibrational spectra of noncrystalline solids exhibit broad bands centered at wavenumbers corresponding to the vibrational modes of the corresponding crystals (Figure 5). In silicate glasses shifts in the high-wavenumber bands... 

With the microfocus instrument it is possible to combine the weak Raman scattering of liquid water with a water-immersion lens on the microscope and to determine spectra on precipitates in equilibrium with the mother liquor. Unique among characterization tools, Raman spectroscopy will give structural information on solids that are otherwise unstable when removed from their solutions. 

Raman spectroscopy is a very convenient technique for the identification of crystalline or molecular phases, for obtaining structural information on noncrystalline solids, for identifying molecular species in aqueous solutions, and for characterizing solid—liquid interfaces. Backscattering geometries, especially with microfocus instruments, allow films, coatings, and surfaces to be easily measured. Ambient atmospheres can be used and no special sample preparation is needed. 

Recent developments in Raman equipment has led to a considerable increase in sensitivity. This has enabled the monitoring of reactions of organic monolayers on glassy carbon [4.292] and diamond surfaces and analysis of the structure of Lang-muir-Blodgett monolayers without any enhancement effects. Although this unenhanced surface-Raman spectroscopy is expected to be applicable to a variety of technically or scientifically important surfaces and interfaces, it nevertheless requires careful optimization of the apparatus, data treatment, and sample preparation. 

Raman spectroscopy has provided information on catalytically active transition metal oxide species (e. g. V, Nb, Cr, Mo, W, and Re) present on the surface of different oxide supports (e.g. alumina, titania, zirconia, niobia, and silica). The structures of the surface metal oxide species were reflected in the terminal M=0 and bridging M-O-M vibrations. The location of the surface metal oxide species on the oxide supports was determined by monitoring the specific surface hydroxyls of the support that were being titrated. The surface coverage of the metal oxide species on the oxide supports could be quantitatively obtained, because at monolayer coverage all the reactive surface hydroxyls were titrated and additional metal oxide resulted in the formation of crystalline metal oxide particles. The nature of surface Lewis and Bronsted acid sites in supported metal oxide catalysts has been determined by adsorbing probe mole-... 

The structure of isohypophosphoric acid and its salts can be deduced from nmr which shows the presence of 2 different 4-coordinate P atoms, the absence of a P-P bond and the presence of a P-H group (also confirmed by Raman spectroscopy). It is made by the careful hydrolysis of PCI3 with the stoichiometric amounts of phosphoric acid and water at 50° ... 

Indeed, this is perhaps the earliest example of a new structural species to be established by Raman spectroscopy. (L. A. Woodward, Phil. Mag. 18, 823-7 (1934).)... 

Further benzofuroxan spectra are reported by Gaughran, Picard, and Kaufman, who compare them with benzofurazans, by Boyer et al., who find similarities with furoxans and nitroso compounds, and by others. Hexanitrosobenzene was shown by IR and Raman spectroscopy to exist in the benzotrifuroxan structure. ... 

Pressure-induced phase transitions in the titanium dioxide system provide an understanding of crystal structure and mineral stability in planets interior and thus are of major geophysical interest. Moderate pressures transform either of the three stable polymorphs into the a-Pb02 (columbite)-type structure, while further pressure increase creates the monoclinic baddeleyite-type structure. Recent high-pressure studies indicate that columbite can be formed only within a limited range of pressures/temperatures, although it is a metastable phase that can be preserved unchanged for years after pressure release Combined Raman spectroscopy and X-ray diffraction studies 6-8,10 ave established that rutile transforms to columbite structure at 10 GPa, while anatase and brookite transform to columbite at approximately 4-5 GPa. 

Two kinds of tantalum-containing initial solutions were chosen according to their ionic complex structure. The first one contained mostly TaF6 ions (Ta F = 1 18) while the second was characterized predominantly by TaF72 ions (Ta F = 1 6.5). The ionic composition of the solutions was determined by Raman spectroscopy. 

Though as yet in its infancy, the application of laser Raman spectroscopy to the study of the nature of adsorbed species appears certain to provide unusually detailed information on the structure of oxide surfaces, the adsorptive properties of natural and synthetic zeolites, the nature of adsorbate-adsorbent interaction, and the mechanism of surface reactions. 

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