M?ssbauer spectroscopy and structural analysis of solids

Mössbauer spectroscopy is reviewed as a method of analysis of hyperfine interactions in the solid state. It is sensitive both to the atomic scale and to phase structures. It utilizes the interactions between the hyperfine fields and nuclei in solids measured by a nuclear technique. The importance of various Mössbauer isotopes is discussed, the ⁵⁷Fe being still the most important. Principles of the qualitative determination of the structure sites and/or phase attachment are explained on the basis of the measurement of hyperfine structure parameters (i.e. the isomer (chemical) shift, the quadrupole and magnetic splittings). The role of the hyperfine field distribution determination is stressed, especially the magnetic hyperfine induction distribution in magnetically ordered solids. Conditions are explained for the feasibility of quantitative estimations of site occupancy and phase abundance. With respect to the predominant role of the magnetic hyperfine structure predestinating Mössbauer spectroscopy to be considered simultaneously as a special magnetic measuring technique, examples are chosen from the field of new magnetic materials. For the substituted hexagonal (M-type) ferrites (aimed, e.g., for the perpendicular magnetic recording), Mössbauer determination of the cation site occupancy is discussed. Structural changes in ion implanted Fe-B-based amorphous alloys detected by the hyperfine field distribution are shown. For the magnetically extremely soft FeCuNbSiB alloys, produced by the controlled crystallization of an amorphous ribbon, the estimation of their rather complicated phase composition by the Mössbauer phase analysis is demonstrated.Common enterprise of the Department of Low Temperature Physics with the Institute of Physics and Institute of Inorganic Chemistry, Czech Academy of Sciences, Prague     

Photoelectron spectroscopy and electronic structures of β-diketonate complexes of rare-earth elements

The electronic structures of lanthanide tris(β-diketonate) complexes and their adducts, being of interest as luminophores, were studied by UV photoelectron spectroscopy of vapors and X-ray photoelectron spectroscopy. The spectral regularities identified by the density functional theory revealed the influence of the substitution of the Me groups in the ligands by Bu^t, CF₃, and neutral ligand in the adducts on the electronic structure of the complexing agent from Pr to Lu.     

Friction force spectroscopy of β- and κ-casein monolayers

Friction force spectroscopy (FFS) has been applied to study the tribological properties of β- and κ-casein layers on hydrophobic substrates in aqueous solutions. Nanometer-sized imaging tips were employed. This allowed exerting and determining the high pressures needed to remove the layers and registering the topographic evolution during this process. Both β- and κ-casein layers showed similar and not particularly high initial frictional responses (friction coefficient of ～1 when measured with a silicon nitride tip). The pressures needed to remove the layers were of the same order of magnitude for both proteins, ～10(8) Pa, but slightly higher for those composed of β-casein. The technique has also shown to be useful in studying the two-dimensional lateral diffusion of the proteins and the wear on the layers they form.     

Submillimeter-wave and far-infrared spectroscopy of high-J transitions of the ground and ν2 = 1 states of ammonia

Complete and reliable knowledge of the ammonia spectrum is needed to enable the analysis and interpretation of astrophysical and planetary observations. Ammonia has been observed in the interstellar medium up to J=18 and more highly excited transitions are expected to appear in hot exoplanets and brown dwarfs. As a result, there is considerable interest in observing and assigning the high J (rovibrational) spectrum. In this work, numerous spectroscopic techniques were employed to study its high J transitions in the ground and ν(2)=1 states. Measurements were carried out using a frequency multiplied submillimeter spectrometer at Jet Propulsion Laboratory (JPL), a tunable far-infrared spectrometer at University of Toyama, and a high-resolution Bruker IFS 125 Fourier transform spectrometer (FTS) at Synchrotron SOLEIL. Highly excited ammonia was created with a radiofrequency discharge and a dc discharge, which allowed assignments of transitions with J up to 35. One hundred and seventy seven ground state and ν(2)=1 inversion transitions were observed with microwave accuracy in the 0.3-4.7 THz region. Of these, 125 were observed for the first time, including 26 ΔK=3 transitions. Over 2000 far-infrared transitions were assigned to the ground state and ν(2)=1 inversion bands as well as the ν(2) fundamental band. Of these, 1912 were assigned using the FTS data for the first time, including 222 ΔK=3 transitions. The accuracy of these measurements has been estimated to be 0.0003-0.0006?cm(-1). A reduced root mean square error of 0.9 was obtained for a global fit of the ground and ν(2)=1 states, which includes the lines assigned in this work and all previously available microwave, terahertz, far-infrared, and mid-infrared data. The new measurements and predictions reported here will support the analyses of astronomical observations by high-resolution spectroscopy telescopes such as Herschel, SOFIA, and ALMA. The comprehensive experimental rovibrational energy levels reported here will permit further refinement of the potential energy surface to improve ammonia ab initio calculations and facilitate assignment of new high-resolution spectra of hot ammonia.     

Ultrafast excited state dynamics and spectroscopy of 13,13'-diphenyl-β-carotene

Ultrafast transient broadband absorption spectroscopy based on the Pump-Supercontinuum Probe (PSCP) technique has been applied to characterize the excited state dynamics of the newly-synthesized artificial β-carotene derivative 13,13'-diphenyl-β-carotene in the wavelength range 340-770 nm with ca. 60 fs cross-correlation time after excitation to the S(2) state. The influence of phenyl substitution at the polyene backbone has been investigated in different solvents by comparing the dynamics of the internal conversion (IC) processes S(2)→ S(1) and S(1)→ S(0)* with results for β-carotene. Global analysis provides IC time constants and also time-dependent S(1) spectra demonstrating vibrational relaxation processes. Intramolecular vibrational redistribution processes are accelerated by phenyl substitution and are also solvent-dependent. DFT and TDDFT-TDA calculations suggest that both phenyl rings prefer an orientation where their ring planes are almost perpendicular to the plane of the carotene backbone, largely decoupling them electronically from the polyene system. This is consistent with several experimental observations: the up-field chemical shift of adjacent hydrogen atoms by a ring-current effect of the phenyl groups in the (1)H NMR spectrum, a small red-shift of the S(0)→ S(2)(0-0) transition energy in the steady-state absorption spectrum relative to β-carotene, and almost the same S(1)→ S(0)* IC time constant as in β-carotene, suggesting a similar S(1)-S(0) energy gap. The oscillator strength of the S(0)→ S(2) transition of the diphenyl derivative is reduced by ca. 20%. In addition, we observe a highly structured ground state bleach combined with excited state absorption at longer wavelengths, which is typical for an "S* state". Both features can be clearly assigned to absorption of vibrationally hot molecules in the ground electronic state S(0)* superimposed on the bleach of room temperature molecules S(0). The S(0)* population is formed by IC from S(1). These findings are discussed in detail with respect to alternative interpretations previously reported in the literature. Understanding the dynamics of this type of artificial phenyl-substituted carotene systems appears useful regarding their future structural optimization with respect to enhanced thermal stability while keeping the desired photophysical properties.     

Geometrical structure of benzene and naphthalene: ultrahigh-resolution laser spectroscopy and ab initio calculation

Geometrical structures of the isolated benzene and naphthalene molecules have been accurately determined by using ultrahigh-resolution laser spectroscopy and ab initio calculation in a complementary manner. The benzene molecule has been identified to be planar and hexagonal (D(6h)) and the structure has been determined with accuracies of 2 × 10(-14) m (0.2 mA?; 1 A? = 1 × 10(-10) m) for the C-C bond length and 1.0 × 10(-13) m (1.0 mA?) for the C-H bond length. The naphthalene molecule has been identified to be symmetric with respect to three coordinate axes (D(2h)) and the structure has been determined with comparable accuracies. We discuss the effect of vibrational averaging that is a consequence of zero-point motions on the uncertainty in determining the bond lengths.     

Raman and infrared spectroscopy of α and β phases of thin nickel hydroxide films electrochemically formed on nickel

The present work utilizes Raman and infrared (IR) spectroscopy, supported by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) to re-examine the fine structural details of Ni(OH)(2), which is a key material in many energy-related applications. This work also unifies the large body of literature on the topic. Samples were prepared by the galvanostatic basification of nickel salts and by aging the deposits in hot KOH solutions. A simplified model is presented consisting of two fundamental phases (α and β) of Ni(OH)(2) and a range of possible structural disorder arising from factors such as impurities, hydration, and crystal defects. For the first time, all of the lattice modes of β-Ni(OH)(2) have been identified and assigned using factor group analysis. Ni(OH)(2) films can be rapidly identified in pure and mixed samples using Raman or IR spectroscopy by measuring their strong O-H stretching modes, which act as fingerprints. Thus, this work establishes methods to measure the phase, or phases, and disorder at a Ni(OH)(2) sample surface and to correlate desired chemical properties to their structural origins.     

Deoxycholate induced tetramer of αA-crystallin and sites of phosphorylation: fluorescence correlation spectroscopy and femtosecond solvation dynamics

Structure and dynamics of acrylodan labeled αA-crystallin tetramer formed in the presence of a bile salt (sodium deoxycholate, NaDC) has been studied using fluorescence correlation spectroscopy (FCS) and femtosecond up-conversion techniques. Using FCS it is shown that, the diffusion constant (D(t)) of the αA-crystallin oligomer (mass ~800 kDa) increases from ~35 μm(2) s(-1) to ~68 μm(2) s(-1). This corresponds to a decrease in hydrodynamic radius (r(h)) from ~6.9 nm to ~3.3 nm. This corresponds to about 10-fold decrease in molecular mass to ~80 kDa and suggests formation of a tetramer (since mass of αA-crystallin monomer is ~20 kDa). The steady state emission maximum and average solvation time (<τ(s)>) of acrylodan labeled at cysteine 131 position of αA-crystallin is markedly affected on addition of NaDC, while the tryptophan (trp-9) becomes more exposed. This suggests that NaDC binds near the cys-131 and makes the terminal region of αA-crystallin exposed. This may explain the enhanced auto-phosphorylation activity of αA-crystallin near the terminus of the 173 amino acid protein (e.g., at the threonine 13, serine 45, or serine 169 and 172) and suggests that phosphorylation at ser-122 (close to cys-131) is relatively less important.     

Rotational and rovibrational spectroscopy of CH3NC of the ground and ν4 = 1 vibrational states

The parallel vibration-rotation band ν(4) of methyl isocyanide (CH(3)NC), with a band center at 944.9 cm(-1), was studied by FTIR spectroscopy between 890 and 980 cm(-1) in order to improve the ground-state rotational constants. Such improvement is essential for the scheduled studies of excited vibrational levels and their mutual anharmonic resonances occurring at higher values of the K rotational number. Ground-state combination differences generated from this band, spanning values of J/K from 0 to 85/13, were combined with rotational data from the literature and newly measured rotational transitions, extending the J/K range from 3/0 up to 31/14, and fitted simultaneously with a fully quantitative reproduction of the data. The infrared data of the ν(4) band were analyzed together with rotational data of the ν(4) = 1 level, spanning values of J/K from 4/0 to 14/12. The fit in the approximation of an isolated vibrational state, with the transitions perturbed by weak local resonances excluded, yields reproduction of the data within experimental uncertainties.     

Vibrational spectroscopy of lapachol, α- and β-lapachone: Theoretical and experimental elucidation of the Raman and infrared spectra

Raman and infrared spectroscopy were applied for the vibrational characterization of lapachol and its pyran derivatives, α-lapachone and β-lapachone. Experimental spectra of solid state samples were acquired between 4000 and 100 cm⁻¹ in Raman experiments, and between 4000 and 600 cm⁻¹ (mid-infrared) and 600–100 cm⁻¹ (far-infrared) with FTIR spectroscopy, respectively. Full structure optimization and theoretical vibrational wavenumbers were calculated at the B3LYP/6-31 + + G(d,p) level. Detailed assignments of vibrational modes in an experimental and theoretical spectra were based on potential energy distribution analyses, using Veda 4.1 software. Clear differentiation between the three compounds was verified in the region between 1725 and 1525 cm⁻¹, in which the ν(CO) and ν(CC) modes of the quinone moiety were assigned.     

Thermal Treatments of Fe—Mn Alkoxide of Glycerol: Infrared absorption and emission spectroscopy

Synthetic Fe—Mn alkoxide of glycerol samples are submitted to controlled heating conditions and examined by IR absorption spectroscopy. On the other hand, the same sample is studied by infrared emission spectroscopy (IRES), upon heating in situ from 100 to 600°C. The spectral techniques employed in this contribution, especially IRES, show that as a result of the thermal treatments ferromagnetic oxides (manganese ferrite) are formed between 350 and 400°C. Some further spectral changes are seen at higher temperatures.This revised version was published online in November 2005 with corrections to the Cover Date.     

Femtosecond spectroscopy of the (2)1Σ u + double minimum state of Na2: time domain and frequency spectroscopy

Femtosecond time resolved pump-probe experiments studying wave packet dynamics in the (2)¹Σ _u ⁺ double minimum state of Na₂ are reported. The experiments were performed in a molecular beam with ion Time of Flight (TOF) detection. By Fast Fourier Transformation (FFT) of the observed time domain data the energy spacings of the coherently coupled vibrational levels in the (2)¹Σ _u ⁺ potential are obtained with an accuracy of 0.02 cm^?1, although an ultrafast laser source with its inherent spectral width was used in the experiment. The wavelengths of the pump and probe laser pulses are chosen such that in this two color experiment we can control ionisation versus ionisation induced fragmentation. In order to study the influence of the potential barrier on a vibrational wave packet motion we performed simulations based on time dependent quantum calculations.     

Determination of the stoichiometry and stability constants of theβ-cyclodextrin-dextromethorphan inclusion complexes by liquid chromatography and UV spectroscopy

The inclosion of dextromethorphan (DMN) by -cyclodextrin (-CD) was studied by using chromatography, UV spectroscopy and circular dichroism methods at 25 °C, pH 7.4 and 4.2. It was found that the CD : DMN complex has 1 : 1 stoichiometry. It is more stable at pH 7.4 than at pH 4.2. with constants respectively equal to 8000 ± 800 M^–1 and 5750 ± 500 M^–i, as determined by chromatography. The stability of the complex at pH 7.4 decreases as the temperature increases. From the van 't Hoff dependence the standard entropy and enthalpy changes were determined at this pH.     

Terahertz time-domain spectroscopy of some pentoses

1 Introduction Terahertz time-domain spectroscopy (THz-TDS) is a new spectral technique based on femto-second laser technology developed since the 1980s[1]. Terahertz (THz) waves lie between the infrared and microwave bands in the electromagnetic spectrum covering the frequency range from 100 GHz to 10 THz. Despite great scientific interest, the THz frequency range re- mains one of the least tapped regions of the electro- magnetic spectrum because there are neither conven- ient high-power…     

Comparison of high-performance liquid chromatography — Mass spectroscopy and capillary electrophoresis— mass spectroscopy for the analysis of phenolic compounds in diethyl ether extracts of red wines

Summary Reversed-phase high-performance liquid chromatography-mass spectroscopy (HPLC-MS) and capillary electrophoresis-mass spectroscopy (CE-MS) have been compared for the analysis of phenolic compounds in diethyl ether extracts of red wines. MS was performed in the electrospray negative-ionization mode. Despite the much higher separation efficiency of CE compared with LC, LC-MS furnishes far superior information for elucidation of the structure of the constituents. LC-MS enabled the identification of twenty-four compounds whereas only thirteen were characterized by CE-MS.     

High-resolution Fourier-transform infrared spectroscopy of the Coriolis coupled ground state and ν7 mode of ketenimine

High resolution FTIR spectra of the short lived species ketenimine have been recorded in the regions 390-1300 cm(-1) and 20-110 cm(-1) using synchrotron radiation. Two thousand six hundred sixty transitions of the ν(7) band centered at 693 cm(-1) and 126 far-IR rotational transitions have been assigned. Rotational and centrifugal distortion parameters for the ν(7) mode were determined and local Fermi and b-axis Coriolis interactions with 2ν(12) are treated. A further refinement of the ground state, ν(12) and ν(8) parameters was also achieved, including the treatment of previously unrecognized ac-axis and ab-axis second order perturbations to the ground state.     

Application of density functional theory and optical spectroscopy for the prediction of the photophysical properties of Р-pyridylphospholanes

Russian Chemical Bulletin - The spatial and electronic structure of a series of pyridyl-containing phospholanes, which are potential ligands for the synthesis of luminescent transition metal...     

High-resolution Fourier transform infrared spectroscopy and analysis of the ν12 fundamental band of ethylene-d4

The Fourier transform infrared (IR) spectrum of the ν₁₂ fundamental band of ethylene-d₄ (C₂D₄) has been measured with an unapodized resolution of 0.004 cm⁻¹ in the frequency range of 1030–1130 cm⁻¹. A total of 1340 assigned transitions have been analyzed and fitted using a Watson's A-reduced Hamiltonian in the I^r representation to derive rovibrational constants for the upper state (v₁₂=1) up to five quartic terms with a standard deviation of 0.00042 cm⁻¹. They represent the most accurate constants for the band thus far. The ground state rovibrational constants were also further improved by a fit of combination–differences from the IR measurements. The relatively unperturbed band was found to be basically A-type with a band centre at 1076.98492±0.00003 cm⁻¹.     

MIR and NIR spectroscopy of sol–gel hydrotalcites with various trivalent cations

Three different hydrotalcites were synthesized from magnesium ethoxide, and aluminium, gallium and indium acetylacetonate, using the sol–gel technique. The colloid suspensions initially obtained were gelled and separated by centrifugation. XRD diffraction patterns confirmed that all solids thus obtained possessed a hydrotalcite structure. The resulting hydrotalcites were characterized by mid-infrared (MIR) and near-infrared (NIR) spectroscopies. The two types of spectra were found not to depend on the synthetic medium or trivalent metal used and were thus quite similar. The MIR spectra for the three solids included a strong band at 3500–3000 cm⁻¹ due to stretching vibrations of the different types of O–H groups in them. The signal at about 1370 cm⁻¹ observed for all solids indicates that the sole interlayer anion present was carbonate. The NIR spectra exhibited the bands for the first and second overtone of the O–H stretching vibration in addition to various combination bands.