Phonon dynamics and electron-phonon coupling in pristine picene

The paper reports a complete analysis of the phonon structure of crystalline picene, a recently announced organic semiconductor. Both lattice and intramolecular vibrations are investigated. An exhaustive assignment of lattice phonons is obtained through polarized Raman spectra assisted by lattice dynamics calculations based on a well tested atom-atom potential model. Raman, infrared spectra and density functional (DFT) calculations are used for the characterization of intramolecular modes. Coupling between low-frequency molecular vibrations and lattice phonons is accounted for. Molecule-to-molecule transfer integrals, as well as the Peierls and Holstein (non-local and local) coupling constants, are evaluated through the semiempirical method INDO/S (Intermediate Neglect of Differential Overlap with Spectroscopic parametrization).     

Raman and infrared spectroscopy of the manganese arsenate mineral allactite

The mineral allactite [Mn(7)(AsO(4))(2)(OH)(8)] is a basic manganese arsenate which is highly pleochroic. The use of the 633 nm excitation line enables quality spectra of to be obtained irrespective of the crystal orientation. The mineral is characterised by a set of sharp bands in the 770-885 cm(-1) region. Intense and sharp Raman bands are observed at 883, 858, 834, 827, 808 and 779 cm(-1). Collecting the spectral data at 77K enabled better band separation with narrower bandwidths. The observation of multiple AsO(4) stretching bands indicates the non-equivalence of the arsenate anions in the allactite structure. In comparison the infrared spectrum shows a broad spectral profile with a series of difficult to define overlapping bands. The low wavenumber region sets of bands which are assigned to the nu(2) modes (361 and 359 cm(-1)), the nu(4) modes (471, 452 and 422 cm(-1)), AsO stretching vibrations at 331 and 324 cm(-1), and bands at 289 and 271 cm(-1) which may be ascribed to MnO stretching modes. The observation of multiple bands shows the loss of symmetry of the AsO(4) units and the non-equivalence of these units in the allactite structure. The study shows that highly pleochroic minerals can be studied by Raman spectroscopy.     

Room-temperature vibrational properties of the BiMn2O5 mullite

Raman and infrared spectroscopic measurements were performed and combined with lattice dynamics simulations in order to describe the room temperature vibrational properties of the BiMn₂O₅ mullite ceramic. A total of 13 Raman active modes and 19 infrared active modes were observed. The lattice dynamics simulation was used to assign the observed bands and to discuss the phonon behavior of this compound. The obtained dielectric constant and unloaded quality factor parameters for BMO ceramic obtained from the infrared data suggest the applicability of the BiMn₂O₅ as a possible candidate to microwave applications.     

Proton dynamics in the hydrogen bond. Inelastic neutron scattering by single crystals of CsH2PO4 at 20 K

Inelastic neutron scattering spectra (INS) of the powder and of oriented single crystals of cesium dihydrogen phosphate (CsH₂PO₄, or CDP) at 20 K have been investigated. For single crystals the incident neutron beam was perpendicular to either the [100] or [001] crystal planes in order to distinguish between the short and long hydrogen bonds. The proposed assignments are based on previous infrared and Raman data and on the INS band intensities and polarisation. The optical and INS OH stretching band profiles are compared. Their shapes are described in terms of mechanical and electrical coupling of the two stretching modes of a O---H…O hydrogen bond. For the longer bond a Fermi resonance of the OH stretching mode with an overtone of the bending mode is observed. Finally, a broad central mode observed in the INS at very low frequency has been tentatively assigned to the relaxation of the proton transfer along the hydrogen bond.     

Laser Raman spectroscopic study of photoreaction dynamics in p -chloro cinnamic acid crystal

Raman phonon spectroscopy has been used to study photodimerization reaction inp-chloro cinnamic acid (pCCA) crystal. The β-form of the crystal yields the 4,4′-dichloro-β-truxinic acid dimer. Six distinct low frequency phonon bands are observed in thepCCA monomer crystal. On reaction progress, these bands show a monotonic shift to lower frequencies and broaden out. Finally, in the dimer crystal the phonon spectrum shows two weak broad bands. These results suggest that the reaction is homogeneous in the initial stages and, as the product concentration increases, the lattice becomes highly disordered. The reactant and the product were characterised by infrared and Raman spectroscopy. The disappearance of aliphatic C=C bond stretching vibration and appearance of cyclobutane ring deformation and cyclobutane ring-breathing vibrations on reaction confirm photodimerization by cyclobutane ring formation. The large Stoke's shift between the absorption and emission band suggest strong exciton-phonon coupling in the monomer lattice. This reaction seems to be phonon-mediated.     

Spectroscopic studies of photochemical reactions in organic solids: Photopolymerization of 1,4 bis[β-pyridyl(2)vinyl] benzene

The laser Raman phonon spectroscopic technique has been used to study the photopolymerization reaction of 1,4 bis[β-pyridyl(2)vinyl] benzene (P2VB). Raman and infrared spectroscopy have been used to study the intramolecular vibrations of the reactant and the product and to characterize them. Absence of any large Stokes' shift between absorption and emission bands of the monomer crystal shows that exciton–phonon coupling is weak, and the reaction is not likely to be phonon mediated. Phonon spectroscopy shows that the reaction proceeds by a heterogeneous mechanism. Sharp phonon bands of the product, however, suggests that the photopoly P2VB lattice is highly ordered.     

Electronic excitations and lattice dynamics of coordinatively "unsaturated" complex transition metal compounds

Single crystal polarized Raman and infrared spectra of the series Na(5)[MO(2)][X] with M = Co(I), Ni(I), and Cu(I) and X = S(2-) and CO(3)(2-), are reported. All phonon modes are assigned to the lattice eigenmodes based on the group theory analysis and first principles lattice dynamics calculations. The energies of the fundamental symmetric and asymmetric vibrations of the [MO(2)](3-) complex are discussed on the basis of their electronic structure and variation in M-O interatomic distances. Electronic Raman scattering and luminescence are observed for the magnetic members of the series (Co(I), d(8), and Ni(I), d(9)). Ligand field theory is employed to account for the electronic effects which originate from states split by spin-orbit coupling.     

Proton dynamics in an extended array of hydrogen bonds: normal coordinates, proton transfer and macroscopic quantum entanglement in the ground state

After a brief introduction to neutron scattering techniques, illustrated with the scattering function for harmonic oscillators, some new aspects of proton dynamics in the KHCO₃ crystal are presented. The full scattering function for the proton modes measured on single crystals provides a graphic view of proton dynamics. Vibrational states are fully characterized with three quantum numbers. The effective oscillator mass of 1 amu confirms the decoupling of protons from the lattice. Combining infrared, Raman and inelastic neutron scattering techniques, the double minimum potential for the transfer of a single proton along hydrogen bonds is totally determined. Elastic neutron scattering techniques probe dynamics in the fully degenerate ground state. Quantum entanglement arising from normal coordinates gives rise to quantum interference. With diffraction techniques, the dynamical structure arising from large-scale quantum coherence is observed as ridges of intensity, well separated from Bragg's peaks. The vibrational wave function in the ground state must be regarded as a superposition of non-factorable macroscopic wave function.     

Infrared and infrared emission spectroscopy of the zinc carbonate mineral smithsonite

Infrared emission and infrared spectroscopy has been used to study a series of selected natural smithsonites from different origins. An intense broad infrared band at 1440cm(-1) is assigned to the nu(3) CO(3)(2-) antisymmetric stretching vibration. An additional band is resolved at 1335cm(-1). An intense sharp Raman band at 1092cm(-1) is assigned to the CO(3)(2-) symmetric stretching vibration. Infrared emission spectra show a broad antisymmetric band at 1442cm(-1) shifting to lower wavenumbers with thermal treatment. A band observed at 870cm(-1) with a band of lesser intensity at 842cm(-1) shifts to higher wavenumbers upon thermal treatment and is observed at 865cm(-1) at 400 degrees C and is assigned to the CO(3)(2-)nu(2) mode. No nu(2) bending modes are observed in the Raman spectra for smithsonite. The band at 746cm(-1) shifts to 743cm(-1) at 400 degrees C and is attributed to the CO(3)(2-)nu(4) in phase bending modes. Two infrared bands at 744 and around 729cm(-1) are assigned to the nu(4) in phase bending mode. Multiple bands may be attributed to the structural distortion ZnO(6) octahedron. This structural distortion is brought about by the substitution of Zn by some other cation. A number of bands at 2499, 2597, 2858, 2954 and 2991cm(-1) in both the IE and infrared spectra are attributed to combination bands.     

Electronic and vibrational spectra of diphenylmethane

From the critical analyses of Raman and infrared spectra, different normal modes of vibration of diphenylmethane (DPM) have been identified. The near ultraviolet absorption spectra of the molecule are found to consist of two band systems, one around 220 nm and the other around 270 nm with respective f-values 5.23 x 10(-2) and 6.44 x 10(-3). The first system is broad and shows few diffuse structures, whereas the later one exhibits very well-resolved structure. They are respectively assigned as 1L(a) and 1L(b) bands. The Raman excitation profiles of several normal modes have been analyzed to get structural and other information of different excited electronic states.     

Raman and infrared spectra of crystalline chloroform

Raman and far-infrared spectra of polycrystalline samples of chloroform at 20 and 80 K are reported. Crystal field spilttings of the intramolecular fundamentals are observed as well as nine Raman and six infrared lattice modes. Spectra are interpreted in terms of a group theoretical analysis based on the molecular and crystal symmetries.     

SUY的晶胞参数和骨架振动频率与其硅铝比间的关系

用SiCl₄(气)高温处理HY制得一系列USY(T),以USY(T)的晶胞常数α₀对其单位晶胞中铝原子的数目作图,发现c₀在24.45～24.55有一断落区间。由实验结果推导出两个以晶胞常数计算USY骨架硅铝比的公式。用400～1500cm^-1范围的红外光谱研究了USY的骨架变化。一些骨架振动特征频率与晶胞常数,单位晶胞中铝原子分数的相关图,也都出现断落区间。当晶胞常数小于24.41时,460cm^-1及1145cm^-1的两个峰发生劈裂。随晶胞常数的减少光谱峰变窄。     

A Raman spectroscopic study of the uranyl sulphate mineral johannite

Raman spectroscopy at 298 and 77K has been used to study the secondary uranyl mineral johannite of formula (Cu(UO2)2(SO4)2(OH)2 x 8H2O). Four Raman bands are observed at 3593, 3523, 3387 and 3234cm(-1) and four infrared bands at 3589, 3518, 3389 and 3205cm(-1). The first two bands are assigned to OH- units (hydroxyls) and the second two bands to water units. Estimations of the hydrogen bond distances for these four bands are 3.35, 2.92, 2.79 and 2.70 A. A sharp intense band at 1042 cm(-1) is attributed to the (SO4)2- symmetric stretching vibration and the three Raman bands at 1147, 1100 and 1090cm(-1) to the (SO4)2- anti-symmetric stretching vibrations. The nu2 bending modes were at 469, 425 and 388 cm(-1) at 77K confirming the reduction in symmetry of the (SO4)2- units. At 77K two bands at 811 and 786 cm(-1) are attributed to the nu1 symmetric stretching modes of the (UO2)2+ units suggesting the non-equivalence of the UO bonds in the (UO2)2+ units. The band at 786cm(-1), however, may be related to water molecules libration modes. In the 77K Raman spectrum, bands are observed at 306, 282, 231 and 210cm(-1) with other low intensity bands found at 191, 170 and 149cm(-1). The two bands at 282 and 210 cm(-1) are attributed to the doubly degenerate nu2 bending vibration of the (UO2)2+ units. Raman spectroscopy can contribute significant knowledge in the study of uranyl minerals because of better band separation with significantly narrower bands, avoiding the complex spectral profiles as observed with infrared spectroscopy.     

Vibrational spectral analysis of L-lysine L-lysinium dichloride nitrate

The infrared and Raman spectra of l-lysine l-lysinium dichloride nitrate were recorded at room temperature and the vibrational assignments of the observed bands were made. The presence of both the carbonyl and ionized carboxylic groups has been identified in the title complex. The lysine and lysinium residues form a dimer through a strong OHO bond between them in the crystal. This together with the different environments has seen by the four –CH₂– groups in each skeleton cause several of the functional group wavenumbers to occur as doublets or as broad bands. Some of the forbidden modes of the nitrate group have been observed. The extensive intermolecular hydrogen bonding in the crystal was identified by the shifting of bands due to the stretching and bending modes of the various functional groups.     

Contributions of symmetric and asymmetric normal coordinates to the intervalence electronic absorption and resonance Raman spectra of a strongly coupled p-phenylenediamine radical cation

Resonance Raman spectroscopy, electronic absorption spectroscopy, and the time-dependent theory of spectroscopy are used to analyze the intervalence electron transfer properties of a strongly delocalized class III molecule, the tetraalkyl-p-phenylene diamine radical cation bis(3-oxo-9-azabicyclo[3.3.1]non-9-yl)benzene ((k33)(2)PD(+)). This molecule is a prototypical system for strongly coupled organic intervalence electron transfer spectroscopy. Resonance Raman excitation profiles in resonance with the lowest energy absorption band are measured. The normal modes of vibration that are most strongly coupled to the intervalence transition are identified and assigned by using UB3LYP/6-31G(d) calculations. Excited state distortions are obtained, and the resonance Raman intensities and excitation profiles are calculated by using the time-dependent theory of Raman spectroscopy. The most highly distorted normal modes are all totally symmetric, but intervalence electron transfer absorption spectra are usually interpreted in terms of a model based on coupling between potential surfaces that are displaced along an asymmetric normal coordinate. This model provides a convenient physical picture for the intervalence compound, but it is inadequate for explaining the spectra. The absorption spectrum arising from only the strongly coupled surfaces consists of a single narrow band, in contrast to the broad, vibronically structured experimental spectrum. The electronic absorption spectrum of (k33)(2)PD(+) is calculated by using exactly the same potential surfaces as those used for the Raman calculations. The importance of symmetric normal coordinates, in addition to the asymmetric coordinate, is discussed. The observed vibronic structure is an example of the missing mode effect; the spacing is interpreted in terms of the time-dependent overlaps in the time domain.     

IR, 1H NMR, mass, XRD and TGA/DTA investigations on the ciprofloxacin/iodine charge-transfer complex

Raman and infrared spectra of two polymorphous minerals with the chemical formula Fe3+(SO4)(OH)·2H2O, monoclinic butlerite and orthorhombic parabutlerite, are studied and the spectra assigned. Observed bands are attributed to the (SO4)2- stretching and bending vibrations, hydrogen bonded water molecules, stretching and bending vibrations of hydroxyl ions, water librational modes, Fe-O and Fe-OH stretching vibrations, Fe-OH bending vibrations and lattice vibrations. The O-H?O hydrogen bond lengths in the structures of both minerals are calculated from the wavenumbers of the stretching vibrations. One symmetrically distinct (SO4)2- unit in the structure of butlerite and two symmetrically distinct (SO4)2- units in the structure of parabutlerite are inferred from the Raman and infrared spectra. This conclusion agrees with the published crystal structures of both mineral phases.     

An infrared and Raman spectroscopic study of some metal pyridine tetracyanonickelate complexes

The results of an infrared and Raman spectroscopic study are presented for seven new metal pyridine tetracyanonickelate complexes, M(py)₂Ni(CN)₄, M = Mn, Co, Fe, Ni, Cu, Zn and Cd. It is shown that the spectra are consistent with a proposed crystal structure for these complexes derived from X-ray diffraction measurements. The spectra can be clearly distinguished from those of analogous Hofmann-type clathrates with which the nickel complex had been previously confused. The copper complex has spectral features different from the other six compounds and an explanation is proposed in terms of a distortion of the general crystal structure due to the Jahn-Teller effect. Analysis of the single, sharp bands of coordinated pyridine offers a method of resolving some difficulties in earlier assignments of the normal modes of the free base. Several modes of coordinated pyridine have upward shifts in frequency compared to those in the free molecule and the shifts are metal dependent. An explanation, supported by a simple normal coordinate analysis on a model, is provided in terms of coupling with low frequency vibrations, particularly the M-N stretching frequency. Other vibrations of the Ni(CN)₄ group, which coordinates to the metals M to form a two-dimensional coordination polymer, are also metal dependent. It is similarly suggested that coupling with low frequency modes is the principal cause of the upward shifts in frequency.     

Jahn-teller splitting of the 3s → 3p transition of sodium isolated in A·Xenon matrix

The rose center in BaF₂ is investigated by resonant Raman scattering. The spectra obtained at liquid-helium temperature show multiple order and combination bands of the internal local modes (up to the sixth order), and associated side bands of the lattice. The temperature dependence of the linewidth of the local-mode transitions has been investigated and is explained as being due to anharmonic coupling to the lattice.     

Infrared and laser Raman studies of bis(L-threoninium) sulphate monohydrate

The infrared and Raman spectra of bis(L-threoninium) sulphate monohydrate crystal have been recorded and analysed at room temperature. The proposed assignment of normal modes is based on group theoretical analysis. There is extensive intermolecular hydrogen bonding in the crystal and this is responsible for the changes in the position and intensity of several bands. The anion fundamentals continue to be degenerated which indicates that its symmetry is unaffected in the molecule.     

Terahertz time-domain and Raman spectroscopy of the sulfur-containing peptide dimers: Low-frequency markers of disulfide bridges

The terahertz time-domain and Raman spectra of sulfur-containing cystein-based peptides in the region of the low-frequency infrared vibrations have been measured at room temperature. The low-frequency bands that can be assigned to the S–S bridges are observed. The vibrational modes found in molecular crystalline materials should be described as phonon modes with strong coupling to the intra molecular vibrations.