Charged-soft-sphere potentials for trivalent metal halides

Summary Octahedral-type coordination by halogens in the liquid state has been reported for a number of trivalent metal ions from diffraction and Raman scattering experiments on their molten trihalides and from Raman scattering spectroscopy of liquid mixtures of trihalides with alkali halides. We analyse the available data on bond lengths and Raman frequencies by treating an isolated (MX₆)³⁻ species within a model which adopts charged-soft-sphere interionic potentials supplemented by an account of ionic polarization. The trivalent metal ions that we consider are M=La, Ce, Pr, Nd, Sm, Gd, Dy and Y for X=Cl and M=Al for X=F. The main result of the analysis is the prediction of trends in the soft-sphere repulsive parameters for the trivalent metal ions, leading to estimates of all the vibrational frequencies and the binding energy of such octahedral species. Due to the relevance of its scientific content, this paper has been given priority by the Journal Direction.     

Infrared and Raman spectra of M2Cu2O5 (M=Y,Ho)

We report both Raman and infrared reflectivity spectra of M₂Cu₂O₅ (M=Y, Ho) at room temperature in the spectral range of 30–1000 cm^–1.37 (31) ir and 18 (15) Raman active modes of Y₂Cu₂O₅ (Ho₂Cu₂O₅) are observed. A factor group analysis has been performed to identify the symmetries of the observed modes. Comparing the vibrational spectra of these compounds we conclude that the phonons above 300 cm^–1 originate from the Cu–O vibrations and those under 300 cm^–1 from M–O vibrations.Alexander von Humboldt Foundation fellow     

Characterization of Ir(ppy)3 and [Ir(ppy)2 bpy]+ by infrared,Raman spectra and surface‐enhanced Raman scattering

The Raman and infrared spectra of fac ‐tris(2‐phenylpyridinato‐N,C2′)iridium(III), Ir(ppy)₃ and surface‐enhanced resonance Raman spectra of bis(2‐phenyl pyridinato‐) (2,2′bipyridine) iridium (III), [Ir(ppy)₂ (bpy)]⁺ cation were recorded in the wavenumber range 150–1700 cm⁻¹, and complete vibrational analyses of Ir(ppy)₃ and [Ir(ppy)₂ (bpy)]⁺ were performed. Most of the vibrational wavenumbers were calculated with density‐functional theory agree with experimental data. On the basis of the results of calculation and comparison of the spectra of both complexes and their analogue [Ru(bpy)₃]²⁺, we assign the vibrational wavenumbers for metal–ligand modes; metal–ligand stretching wavenumbers are 277/307 and 261/236 cm⁻¹ for Ir(ppy)₃, and 311/324, 257/270, 199/245 cm⁻¹ for [Ir(ppy)₂ bpy]⁺. Surface‐enhanced Raman scattering spectra of [Ir(ppy)₂ bpy]²⁺ were measured at two wavelengths on the red and blue edges of the low‐energy metal‐to‐ligand charge‐transfer band. According to the enhanced Raman intensities for the vibrational modes of both ligands ppy and bpy, the unresolved charge‐transfer band is deduced to consist of charge‐transfer transitions from the triplet metal to both ligands ppy and bpy. Copyright © 2010 John Wiley & Sons, Ltd.     

BaTiO3和Ce:BaTiO3单晶的高温喇曼散射研究

从室温至180℃测量了BaTiO₃和Ce:BaTiO₃单晶的偏振喇曼谱,在X(ZZ)Y几何配置下发现了三条频率分别为986,1204和1480cm^-1的新谱线.根据喇曼散射截面的温度依赖关系,确认这些新谱线对应二阶喇曼散射,而A₁(TO)谱中位于275和514cm^-1处的非对称宽峰则属于一阶喇曼散射.在此基础上,对立方相BaTiO₃的喇曼谱和结构相变机制进行了讨论.通过比较B     

Fourier Transform Infrared and Raman Spectra of Metal Halide Complexes of 3,5-Lutedine in Relation to Their Structures

Abstract

Fourier transform infrared (4000-200 cm¹) and Raman (3500-50 cm^?1) spectra are reported for metal(II) halide 3,5-lutidine (3,5-dimethylpyridine) complexes of the following stoichiometries: M(3,5L)₄X₂ M=Co or Ni, X=C1 or Br; M=Mn or Cu, X=Br; M=Cd, X=I; M(3,5L)₃X₂ M=Fe, X=C1; M=Cu, X=Br; Hg(3,5L) X₂ X=C1 or Br.

Vibrational assignments are given for all the observed bands. Some structure- spectra correlations are found. For a given series of isomorphous complexes the sum of the difference between the liquid and ligand values of the vibrational modes of 3,5-lutidine is found to increase in the order of the second ionization potentials of the metals. The frequency shifts are also found to depend on the halogen.     

Fourier Transform Infrared and Raman Spectra of 4-Vinylpyridine and its Transition Metal(II) Tetracyanonickelate Complexes

Abstract

Infrared and Raman spectra (4000-200 cm^?1) were recorded for 4-vinylpyridine and vibrational assignments made for fundamental modes on the basis of frequency shifts of the coordinated ligand, of the group vibrational concept and comparison with the assignments for related molecules. the infrared spectra of M(4-vinylpyridine)₂Ni(CN)₄ (M=Mn, Cd, Fe, Co, Ni or Cu) are reported.     

Raman spectroscopy of CaM2+Ge2O6 (M2+ = Mg,Mn, Fe,Co, Ni,Zn) clinopyroxenes

The Raman spectra of Ge‐clinopyroxenes CaM²⁺Ge₂O₆ (M²⁺ = Mg, Mn, Fe, Co, Ni, Zn), general formula M2M1T₂O₆, are reported for the first time. Their spectral features are discussed in comparison with corresponding Si‐pyroxenes. The vibrational wavenumbers of germanates may be roughly obtained by a scale factor of about ~0.8 by those of the corresponding silicates, due to the Ge‐Si mass difference. The main peaks in the germanate Raman spectra at ~850 and ~540 cm⁻¹ may be related to Ge‐O tetrahedral stretching and chain bending, respectively; minor peaks between 200 and 400 cm⁻¹ are ascribed to bending and stretching of the non‐tetrahedral cations. Within Ge‐pyroxenes, possible correlations between crystallographic parameters and the vibrational wavenumbers are investigated. The main stretching mode at ~850 cm⁻¹ shows wavenumber changes with M²⁺ substitutions, but no simple correlation can be found with M²⁺ cation mass or size. On the other hand, the chain bending wavenumber linearly decreases with increasing ionic radius of the M²⁺ cation: the expansion of the M1 polyhedron reduces the chain kinking angle and the Ge‐Ge distances correspondingly increase. Copyright © 2015 John Wiley & Sons, Ltd.     

Infrared Spectrum of Dihydridobis(ethylenediamine) Osmium Tetrachloro Zincate

The ethylenediamine trmsition metal complexes^1-9 of the type M(en)₂X₂ (M = Co, Ni, Cu, Pd, Pt and × = I, Br, C1, NO³, C10⁴) have infrared spectra of complicated nature which have been used for the study of conformation of the chelate ring. In dihydrldobis ZnC14 ethylenediamlne transition metal complexes, the hydrogen bonding and the presence of ZnCl₄ further complicates the vibrational spectra. With a view to study this, the present study of dihydridobis (ethylenedianlne) osnlum tetrachloro zincate was carried out.     

Theoretical calculations of vibrational modes in endohedral metallofullerenes: La@C82 and Sc2@C84

Density functional theory at the B3LYP level is applied to representative mono- and dime-tallofullerenes, La@C₈₂ and Sc₂@C₈₄, to calculate the metal-cage vibrational modes that are currently of considerable interest in far-infrared and Raman spectroscopic studies. The La based vibrations calculated for La@C₈₂ are in good agreement with those assigned experimentally. The vibrational frequencies are little changed upon reduction and oxidation. The Sc based vibrations calculated for Sc₂@C₈₄ are also compared with the available experimental data. In addition, the structures of the isomers of Sc₂@C₈₄ are discussed. Electrostatic interactions play an important role in endohedral metallofullerenes.     

Synthesis and structural characterization of a series of lanthanide stannate pyrochlores

A simple hydrothermal method has been employed to prepare a series of lanthanide stannate pyrochlores Ln₂Sn₂O₇ (Ln=Y, La, Pr-Yb) at a relatively low temperature of less than 200 °C successfully. On the basis of structural characterizations by X-ray powder diffraction (XRD), Fourier transform infrared (FT-IR) absorption spectroscopy and Raman spectroscopy, it was found that the positions of bands in vibrational spectra are sensitive to the ionic radius of Ln³⁺, and the linear relationship can be seen between the frequency of Sn-O stretching mode and the lanthanide ionic radius in IR spectrum, as well as the frequency of O-Sn-O bending mode and the lanthanide ionic radius in Raman spectrum.     

Deposition of endohedral fullerenes from a laser evaporation cluster source

Mass spectra of fullerenes doped with transition and rare earth metals (Sc, Y, La, Ce, Gd) reveal a variety of singly and doubly doped metallofullerenes. Characteristic oscillations of the relative mass intensities of the La- and Y-metallofullerenes suggest the existence of two different isomers of the corresponding doubly doped fullerenes. The yield of the plasma-generated clusters is sufficient to be used for an in situ deposition of mass-selected metallofullerenes onto a surface. In particular, endohedral fullerenes with 60 or less atoms are accessible for deposition by means of a laser vaporization cluster source. Scanning tunneling microscopy has been used to image Ce@C₆₀ and La@C₆₀ on highly oriented pyrolytic graphite. Received: 24 May 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001     

Molecular structure,spectroscopic (FTIR,FTIR gas phase,FT‐Raman) first‐order hyperpolarizability and HOMO–LUMO analysis of 4‐methoxy‐2‐methyl benzoic acid

Vibrational spectral analysis was carried out for 4‐methoxy‐2‐methyl benzoic acid (4M2MBA) by using Fourier transform infrared (FT‐IR) (solid, gas phase) and FT‐Raman spectroscopy in the range of 400–4000 and 10–3500 cm⁻¹ respectively. The effects of molecular association through O H···O hydrogen bonding have been described by the single dimer structure. The theoretical computational density functional theory (DFT) and Hatree‐Fock (HF) method were performed at 6–311++G(d,p) levels to derive the equilibrium geometry, vibrational wavenumbers, infrared intensities and Raman scattering activities. The scaled theoretical wavenumbers were also shown to be in good agreement with experimental data. The first‐order hyperpolarizability (β₀) of this novel molecular system and related properties (β, α₀ and Δα) of 4M2MBA are calculated using the B3LYP/cc‐pvdz basis set, based on the finite‐field approach. A detailed interpretation of the infrared and Raman spectra of 4M2MBA is reported. The theoretical spectrograms for FT‐IR and FT‐Raman spectra of the title molecule were also constructed and compared with the experimental one. Copyright © 2010 John Wiley & Sons, Ltd.     

Electric conduction properties of M@C2n endohedral metallofullerenes (M=La, Y)

The electrical conduction properties of powder samples of M@C_2n endohedral metallofullerenes (M=La, Y) isolated from soot by extraction with N,N-dimethylformamide and by sublimation were studied. It was established that the conductivity of sublimated samples exceeded that of the extracted ones by four orders of magnitude and was as high as 0.2–0.5 Ω^?1 cm^?1 at room temperature.     

The Infrared and Raman Spectra of 4-Phenylpyridine and Its Hofmann Type Complexes.

Abstract

The Infrared and Raman spectra of 4-Phenylpyridine are reported for the first time in the 4000-400cm^?1 range. Vibrational assignments have been made for fundamental modes on the basis of frequency shifts of coordinated legend, infrared and Raman band contours and comparisons with the assignments for related molecules. The infrared spectra of M (4-Phenylpyridine) Ni(CN)₄ complexes (M=Mn, Ni or Cd) are reported. Their structure consists of polymeric layers of [M-Ni(CN)₄]_∞ with the 4-phenylpyridine molecules bound to metal (M), similar to the structure found in Hoffmann type host complexes.     

Structural modifications of GaN after cerium implantation

Among the family of rare earth (RE) dopants, the doping of first member Ce into GaN is the least studied system. This article reports structure properties of Ce‐doped GaN realized by technique of ion implantation. Ce ions were implanted into metal organic chemical vapor deposition grown n‐ and p‐GaN/sapphire thin films at doses 3 × 10¹⁴ and 2 × 10¹⁵ cm⁻². X‐ray diffraction scans and Raman scattering measurements exhibited expansion of lattice in the implanted portion of the samples. First order Raman scattering spectra show appearance of several disorder‐activated Raman scattering modes in addition to typical GaN features. A dose‐dependent decrease in intensity of E₂ mode was observed in Raman the spectra of the implanted samples. Ultraviolet Raman spectra of implanted samples show complete quenching of photoluminescence emission and appearance of multiple A₁(LO) phonon scattering modes up to fifth order. Moreover, a decrease in intensity and an increase in line width of LO modes as a function of wavenumber were observed for implanted samples. Copyright © 2012 John Wiley & Sons, Ltd.     

Involvement of weak C?H···X hydrogen bonds in metal‐to‐semiconductor regime change in one‐dimensional organic conductors (o‐DMTTF)2X (X = Cl,Br, and I): combined IR and Raman studies

We report on the infrared (IR) and Raman studies of the three isostructural quasi‐one‐dimensional cation radical salts of 3,4‐dimethyl‐tetrathiafulvalene (o‐DMTTF)₂X (X = Cl, Br, and I), which all exhibit metallic properties at room temperature and undergo transitions to a semiconducting state in two steps: a soft metal‐to‐semiconductor regime change in the temperature region T_ρ = 5–200 K and then a sharp phase transition at about T_MI = 50 K. Polarized IR reflectance spectra (700–16 000 cm⁻¹) and Raman spectra (50–3500 cm⁻¹, excitation λ = 632.8 nm) of single crystals were measured as a function of temperature (T = 5–300 K) to assess the eventual formation of a charge‐ordered state below 50 K. Additionally, the temperature dependence of the IR absorption spectra of powdered crystals in KBr discs was also studied. The Raman spectra and especially the bands related to the CC stretching vibration of o‐DMTTF provide unambiguous evidence of uniform charge distribution on o‐DMTTF down to the lowest temperatures, without any modification below 50 K. However, the temperature dependence of Raman spectra indicates a regime change below about 200 K. Temperature dependence of both electronic dispersion and vibrational features observed in the IR spectra also clearly confirms the regime change below about 200 K and shows the involvement of C H···X hydrogen bonds in the electronic localization; some spectral changes can be also related with the phase transition at 50 K. Additionally, using density functional theory methods, the normal vibrational modes of the neutral o‐DMTTF⁰ and cationic o‐DMTTF⁺ species, as well as their theoretical IR and Raman spectra, were calculated. The theoretical data were compared with the experimental IR and Raman spectra of neutral o‐DMTTF molecule. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman microscopy of haidingerite Ca(AsO3OH)·H2O and brassite Mg(AsO3OH)·4H2O

Raman spectroscopy has been used to study the arsenate minerals haidingerite Ca(AsO₃OH)·H₂O and brassite Mg(AsO₃OH)·4H₂O. Intense Raman bands in the haidingerite spectrum observed at 745 and 855 cm⁻¹ are assigned to the (AsO₃OH)²⁻ν₃ antisymmetric stretching and ν₁ symmetric stretching vibrational modes. For brassite, two similarly assigned intense bands are found at 809 and 862 cm⁻¹. The observation of multiple Raman bands in the (AsO₃OH)²⁻ stretching and bending regions suggests that the arsenate tetrahedrons in the crystal structures of both minerals studied are strongly distorted. Broad Raman bands observed at 2842 cm⁻¹ for haidingerite and 3035 cm⁻¹ for brassite indicate strong hydrogen bonding of water molecules in the structure of these minerals. OH···O hydrogen‐bond lengths were calculated from the Raman spectra based on empirical relations. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the phosphate mineral churchite‐(Y) YPO4·2H2O

Raman spectroscopy has been used to study the rare‐earth mineral churchite‐(Y) of formula (Y,REE)(PO₄) ·2H₂O, where rare‐earth element (REE) is a rare‐earth element. The mineral contains yttrium and, depending on the locality, a range of rare‐earth metals. The Raman spectra of two churchite‐(Y) mineral samples from Jáchymov and Medvědín in the Czech Republic were compared with the Raman spectra of churchite‐(Y) downloaded from the RRUFF data base. The Raman spectra of churchite‐(Y) are characterized by an intense sharp band at 975 cm⁻¹ assigned to the ν₁ (PO₄³⁻) symmetric stretching mode. A lower intensity band observed at around 1065 cm⁻¹ is attributed to the ν₃ (PO₄³⁻) antisymmetric stretching mode. The (PO₄³⁻) bending modes are observed at 497 cm⁻¹ (ν₂) and 563 cm⁻¹ (ν₄). Some small differences in the band positions between the four churchite‐(Y) samples from four different localities were found. These differences may be ascribed to the different compositions of the churchite‐(Y) minerals. Copyright © 2009 John Wiley & Sons, Ltd.     

Pulsed ESR investigations of anisotropic interactions in M@C82 (M=Sc,Y,La)

82 , Y@C₈₂, and La@C₈₂ in frozen solutions. We were able to determine the g tensors of these molecules by analysing magnetic field spectra at X-band (9.5 GHz) and W-band (94 GHz) frequencies. Moreover, in Y@C₈₂ we have investigated the hyperfine interaction of the ⁸⁹Y nuclear spin (I=1/2) with the electron spin on the C₈₂ cage. The principal values of the hyperfine tensor A and the relative orientation of g and A tensors were determined by applying three- and four-pulse electron spin echo envelope modulation techniques (ESEEM). Received: 3 September 1997/Accepted: 10 November 1997     

Metal–metal bonding and structures of trinickel and tricobalt dipyridylamido complexes from surface‐enhanced Raman spectra

We recorded surface‐enhanced Raman scattering (SERS) spectra of metal‐string complexes Co₃(dpa)₄ Cl₂ [di(2‐pyridyl)amido (dpa)], Ni₃(dpa)₄ Cl₂ and the oxidized form of the Ni₃ complex to determine their vibrational wavenumbers and to investigate their structures. For SERS measurements these complexes were adsorbed on silver nanoparticles in aqueous solution to eliminate the constraint of a crystal lattice and the complexes remain in thermal equilibrium. From our analysis of the vibrational normal modes we assigned the SERS lines at 242 and 276 cm⁻¹ to Ni₃ and Co₃ symmetric‐stretching modes of the symmetric form. For Co₃ (dpa)₄Cl₂ a Raman line at 383 cm⁻¹ was assigned to the Co Co stretching mode of the unsymmetric form. The wavenumber of the Ni₃ symmetric‐stretching mode of the oxidized form [Ni₃(dpa)₄]³⁺ is 274 cm⁻¹, greater than that for neutral Ni₃(dpa)₄Cl₂, in agreement with a prediction of delocalized molecular‐orbital theory that an electron is removed from an antibonding orbital after oxidation. The experimental data show that the SERS technique serves as an excellent tool to observe the variation of metal–metal bonding during an oxidation or reduction reaction. Copyright © 2010 John Wiley & Sons, Ltd.