Analysis of high temperature ammonia spectra from 780 to 2100 cm

A recently-recorded set [Hargreaves et al., Astrophys. J., in press] of Fourier transform emission spectra of hot ammonia is analyzed using a variational line list. Approximately 3350 lines are newly assigned to mainly hot bands from vibrational states as high as v₂ = 2. 431 new energy levels of these states are experimentally determined, considerably extending the range of known rotationally-excited states. Comparisons with a recent study of high J levels in the ground and first vibrational states [Yu et al., J. Chem. Phys., 133 (2010) 174317] suggests that while the line assignments presented in that work are correct, their energy level predictions suffer from problems associated with the use of very high-order perturbation series in the effective Hamiltonian. It is suggested that variational calculations provide a more stable method for analyzing spectra involving highly-excited states of ammonia.     

Spontaneous Raman scattering: a useful tool for investigating the afterglow of nanosecond scale discharges in air

Nanosecond scale discharges are considered an interesting way for assisting combustion by enhancing either flame stabilization or ignition. Better understanding of energy deposit and radical species production processes is still required under pressure conditions normally encountered in combustion. The purpose of the present paper is to show that spontaneous Raman scattering, seldom used to investigate nanosecond pulsed discharges, is a useful measurement method for investigating the energy deposit of these discharges. The advantage of spontaneous Raman scattering is described by analyzing N₂ and O₂ spectra during the post-discharge of a filamentary nanosecond air discharge under atmospheric pressure, using phase-locked average spectra. The main advantages of spontaneous Raman scattering measurements are that they allow line-wise probing of different species with the same experimental setup and the determination of vibrational distribution by comparison with theoretical modeling over a wide range of vibrational levels (from v=0 to v=20 for N₂). The model proposed takes into account the high level of vibrational excitation and the strong non-equilibrium observed, allowing the characterization of the vibrational relaxation over the complete post-discharge duration. Although the rotational structure is not resolved, the rotational temperature and thus translational temperature are determined with a moderate uncertainty for T above 500 K.     

Infrared Spectroscopy of the ν1 Band of Sulfur Tetrafluoride, SF4

Infrared absorption spectra of the ν₁ axial S-F stretching vibrational bands of sulfur tetrafluoride, SF₄, have been recorded and analyzed. A diode-laser jet spectrometer was used to record high-resolution spectra of ³²SF₄, with 87 vibration-rotation lines of the ν₁ fundamental being assigned. Least-squares fitting of the data yielded a precise vibrational band origin, as well as rotational parameters for the upper state. In addition, lower-resolution spectra of a static sample of SF₄ held at room temperature were recorded using a Fourier transform (FTIR) spectrometer. The progressions of prominent features observed in the room-temperature FTIR spectra are attributed to summation bands arising from ν₁ transitions from excited vibrational levels of the low-frequency ν₄ manifold of both ³²SF₄ and ³⁴SF₄.     

Higher ro-vibrational levels of H2O deduced from high resolution oxygen-hydrogen flame spectra between 6200 and 9100 cm-1

The spectra of hydrogen-oxygen and acetylene-oxygen flames have been recorded on a Fourier transform spectrometer in the region 6200–9100 cm^-1 with a resolution of 0·015 cm^-1. In this region, we have performed a detailed analysis of the 2v ₂ + v ₃, v ₁ + v ₃, v ₁ + v ₂ + v ₃ - v ₂ and v ₁ + v ₂ + v ₃ bands. A primary motive for this study was to obtain higher rotational energy levels for the (021), (101) and (111) vibrational states. Moreover an extensive set of rotational levels of the (010) vibrational state has been deduced from the combined study of hot bands involving the (011), (021) and (111) vibrational states. A room-temperature absorption spectrum of water recorded on a Fourier transform spectrometer in the region 1750–2300 cm^-1 (resolution 0·005 cm^-1) has also been used to confirm the analysis.     

Matrix‐isolation IR spectroscopy of R‐(+)‐3‐methylcyclopentanone in para‐hydrogen crystal

High‐resolution infrared (IR) spectra of R‐(+)‐3‐methylcyclopentanone (R3MCP) in para‐hydrogen (pH₂) crystal were recorded and compared with the corresponding IR spectra of R3MCP in Argon (Ar) isolation matrix as well as the IR spectra of the neat crystalline R3MCP at low deposition temperature of 4 ± 0.05 K. Moreover, IR spectra of R3MCP, hosted in pH₂ crystal, were recorded using a high‐resolution Fourier transform IR spectrometer as a function of sample concentration and over the range 10–300 ppm. Furthermore, density functional theory calculations of simulated IR spectra for the optimized geometries of R3MCP equatorial‐methyl and axial‐methyl conformers are compared with experimental spectra for the purpose of investigating molecular conformation. Upon comparison between theoretical and experimental IR spectra, vibrational modes arising from equatorial and axial conformers have been successfully assigned and related to the individual conformer's structure. Copyright © 2015 John Wiley & Sons, Ltd.     

Spectroscopy of phonon and vibronic states of YbAl3(BO3)4 single crystal

The polarized Raman and reflection spectra of a single crystal YbAl₃(BO₃)₄ at room temperature were studied. Raman active vibrational modes A ₁, E _TO, and E _LO are identified. In the Raman spectrum, we detected an intense line at a frequency of 1018 cm⁻¹, which refers to internal vibrations of the BO₃ group and is known to be promising for use in amplifiers based on stimulated Raman scattering. From the simulation of reflection spectra by the method of dispersion analysis the frequencies of A ₂ vibrational modes were determined. Intense bands observed in the low-temperature transmission spectra in the range of f-f transitions in the Yb³⁺ ion are attributed to electron-phonon transitions. The Raman lines are compared with electron-phonon lines in the transmission spectrum.     

The Rotational Analysis of the Five new Vibronic Bands of No2 in the Range 5050-5200 Å

The five new vibrational bands in the range 5050-5200 Å of the laser induced fluorescence excitation spectra of NO₂ were measured and rotationally assigned at room temperature. Though the spectra were rather congested, we can determine the band origins, and rotational and spin-rotation constants for these bands. All rotational structures analyzed are of the parallel type. It was shown that the electronic excited state òB₂ were heavily perturbed by the high lying vibration levels of ground state [Xtilde] ² A ₁ and that the interactions between these two electronic states was the main rationale for the complexity of NO₂ visible spectra.     

The absorption spectrum of 12C2H2 IV. The regions 7600–9200 cm−1 and 10600–11500 cm−1

The absorption spectrum of ¹²C₂H₂ has been recorded by intracavity laser absorption spectroscopy (ICLAS) in the 10600–11 500 cm^?1 spectral region, where no absorption bands were previously reported. Fifteen bands starting from the vibrational ground state are observed and rotationally analysed. All corresponding excited vibrational levels were assigned using the polyad model, the so-called cluster model (El Idrissi, M.I., Liévin, J., Campargue, A., and Herman, M., 1999, J. chem. Phys., 110, 2074) which allows vibrational energies, rotational B_v constants and, to some respect, relative band intensities to be predicted. Additional data and constants are also provided in the range 7600–9200cm^?1, whenever improving the literature results, from spectra recorded previously at ULB using Fourier transform spectroscopy. The assignment procedure in the range recorded by ICLAS is detailed, leading to a deeper understanding of vibration-rotation and intensity features of the absorption bands within the frame of the cluster model.     

Simulation of emission spectra of the gas-discharge plasma of a krypton-xenon mixture

The narrow-band radiation observed in the range of the resonance line of xenon at 147 nm in the VUV emission spectra of the gas-discharge plasma of a krypton-xenon mixture is proposed to interpret as a manifestation of bound-bound transitions between the vibrational levels of the excited electronic states 0⁺(³ P ₁) and 1(³ P ₁) and the ground electronic state 0⁺(¹ S ₀) in the KrXe* molecule. A correction of the potential curves of the electronic states under consideration is proposed from a comparison of the calculated and experimental spectra.     

The ν1 and ν3 Bands of the OOO Isotopomer of Ozone

Using 0.002 cm⁻¹ resolution Fourier transform absorption spectra of an ¹⁷O-enriched ozone sample, an extensive analysis of the ν₃ band together with a partial identification of the ν₁ band of the ¹⁷O¹⁶O¹⁷O isotopomer of ozone has been performed for the first time. As for other C_2v-type ozone isotopomers [J.-M. Flaud and R. Bacis, Spectrochim. Acta, Part A 54, 3–16 (1998)], the (001) rotational levels are involved in a Coriolis-type resonance with the levels of the (100) vibrational state. The experimental rotational levels of the (001) and (100) vibrational states have been satisfactorily reproduced using a Hamiltonian matrix which takes into account the observed rovibrational resonances. In this way precise vibrational energies and rotational and coupling constants were deduced and the following band centers ν₀(ν₃) = 1030.0946 cm⁻¹ and ν₀(ν₁) = 1086.7490 cm⁻¹ were obtained for the ν₃ and ν₁ bands, respectively.     

Simulation of Raman spectra of C and C by non-orthogonal tight-binding molecular dynamics

A non-orthogonal tight-binding molecular-dynamics formalism is used to simulate Raman spectra of the fullerene molecules C₆₀ and C₇₀. Two parametrization schemes for the Hamiltonian and the overlap matrix elements are investigated. The considered molecules are excited randomly and the Fourier transform of the displacement autocorrelation function is employed to extract the vibrational properties. Fair agreement with experiment and with force-constant and ab initio calculations is achieved, with comparatively smaller maximum errors in the frequencies than for other molecular dynamics or semi-empirical calculations from the literature. Received 4 February 1999 and Received in final form 28 November 1999     

Raman spectroscopic study of structural disordering in YVO<Subscript>4</Subscript>, GdVO<Subscript>4</Subscript>, and CaWO<Subscript>4</Subscript> crystals

The Raman spectra of single-crystal YVO₄, GdVO₄, and ZrSiO₄ with a zircon structure, as well as CaWO₄ and BaWO₄ with a scheelite structure, are studied in detail over a wide temperature range 14–800 K. An inhomogeneous splitting of the A _1g (ν₂) vibrational lines in the Raman spectra of YVO₄ and GdVO₄ and the A _g (ν₁) vibrational lines in the spectrum of CaWO₄ is detected. It is shown that the profiles of these lines can be decomposed into two components, whose integrated intensities are redistributed with temperature and also depend on the matrix kind in which they are detected. The phenomenon observed is associated with the thermally activated processes of disorientation of the tetrahedral anions in the zircon and scheelite structures.     

Fine band structure of the vibrational spectra of fullerite C<Subscript>60</Subscript> and enhancement of intermolecular interaction in high-temperature phase

The fine structure of the fundamental vibrational bands and some combination tones of fullerite C₆₀ in its IR absorption and reflection spectra, as well as in Raman spectra, has been studied. This structure is due to the overlapping components of Davydov and isotopic splittings and the removal of vibrational degeneracy with symmetry lowering. It is shown that for IR F _u (i) bands (i = 1–4) and low-frequency H _g (1) and A _g (1) bands in the Raman spectrum the splittings at room temperature exceed those for the low-temperature phase. The enhancement of intermolecular interaction at elevated temperatures is explained by the nonequilibrium vibrational excitation of the medium as a result of nonlinear interaction of vibrational modes and by the change in the electronic states.     

The Influence of Temperature on Coumarin 153 Fluorescence Kinetics

The influence of temperature varied in the range 183 K–323 K on the fluorescence quantum yield, fluorescence lifetime, absorption and emission transition moments and non-radiative deactivation rate was determined for the well known and largely used dye Coumarin 153, dissolved in 1-chloropropane. The Kennard-Stepanov relation connecting the absorption and emission spectra was used to check for the presence of more than one absorbing/emitting species and to investigate whether intramolecular vibrational redistribution completes in the C153 excited S ₁ state before the emission takes place. The emission spectrum corresponding to S ₁→S ₀ transition, was fitted at each temperature to the model function including the information on the dye vibrational modes coupling. In this way the displacement in equilibrium distance for the most active vibrational mode was determined for C153 in S ₁ and in S ₀. Using the temperature dependence of the fluorescence decay time and quantum yield, the non-radiative deactivation rate was determined. Its temperature dependence was compared to that calculated using the theoretical model with the most active vibrational mode displacement values taken from steady-state spectra analysis. The somewhat surprising dependence of the fluorescence decay time and quantum yield on temperature was related to non-trivial coupling between low-frequency vibrational modes of C153 in the excited and ground states.     

High-resolution Fourier-transform infrared spectroscopy of the ν1 and ν8 fundamental bands of sulphur tetrafluoride (SF4)

The vibration-rotation spectra of the ν₁ and ν₈ fundamental bands of ³²SF₄ have been observed using Fourier-transform infrared spectroscopy. The band centre of the c-type ν₁ symmetric sulphur-equatorial-fluorine stretching vibration was observed at 891.6 cm^?1 and that for the b-type ν₈ asymmetric sulphur-equatorial-fluorine stretching vibration at 864.6 cm^?1. In total, 2044 rovibrational transitions have been assigned. Analysis of the spectra showed that the rotational states of the ν₁ = 1 and ν₈ = 1 upper vibrational levels are coupled by an a-type Coriolis interaction. This coupling has been treated both using perturbation theory and by the explicit inclusion of an appropriate Hamiltonian matrix element in a combined fit of the data for both bands. Spectroscopic parameters have been determined for the ground, ν₁ = 1 and ν₈ = 1 vibrational levels. Weaker transitions resulting from difference bands and the fundamental bands of the ³⁴SF₄ isotopomer have been identified but could not be assigned, because of the density of lines in the room-temperature spectrum. The possibility that discrepancies between the observed and predicted spectra of the ν₁ fundamental may result from either a Coriolis interaction with the states of another vibrational level, or the effects of intramolecular exchange of axial and equatorial fluorine atoms is considered. The discussion is supported by theoretical calculations which show that the likely path for intramolecular exchange is via a C _4v transition state.     

Experimental and theoretical structure and vibrational analysis of ethyl trifluoroacetate,CF3CO2CH2CH3

The molecular structure and conformational properties of ethyl trifluoroacetate, CF₃CO₂CH₂CH₃, were determined in the gas phase by electron diffraction, and vibrational spectroscopy (IR and Raman). The experimental investigations were supplemented by ab initio (MP2) and DFT quantum chemical calculations at different levels of theory. Experimental and theoretical methods result in two structures with C_s (anti–anti) and C₁ (anti–gauche) symmetries, the former being slightly more stable than the latter. The electron‐diffraction data are best fitted with a mixture of 56% anti–gauche and 44% anti–anti conformers. The conformational preference was also studied using the total energy scheme, and the natural bond orbital scheme. Also, the infrared spectra of CF₃CO₂CH₂CH₃ are reported for the gas, liquid and solid states, as is the Raman spectrum of the liquid. The comparison of experimental averaged IR spectra of C_s and C₁ conformers provides evidence for the predicted conformations in the IR spectra. Harmonic vibrational wavenumbers and scaled force fields have been calculated for both conformers. Copyright © 2009 John Wiley & Sons, Ltd.     

Laser-Induced Fluorescence from CuCl2in a Free-Jet Expansion: High-Resolution Fourier Transform Spectra

High-resolution Fourier transform spectra of the laser-induced fluorescence of copper dichloride produced in a free-jet expansion are presented. The supersonic molecular beam produces rotational cooling and a nearly collision-free environment. Dispersed fluorescence spectra are found to be free of the continuum which restricted the data obtainable with a classical source (hot cell). The reduction in thermal emission allows the fluorescence to be recorded from the laser line (585 nm) out to 1.3 μm, revealing many new vibrational levels of CuCl₂in its ground electronic state,X²Π_g(3/2).     

Vibrational intensity distributions in the photoelectron spectrum of hydrogen

The intensity distribution over the H₂⁺ vibrational levels up to v = 15 has been measured for H₂ photoelectron spectra at a photon wavelength of 584 Å. The data show reasonable agreement with recent calculations only in the range v = 0 through 8; the higher levels are populated significantly lower than predicted by theory.     

Vibrational analysis of 1-chlorooctane

The organic compound 1-chlorooctane exists in liquid state at ambient temperatures and has numerous synthetic applications. Fourier transform infrared and Raman spectra of this molecule have been recorded in the range of 4000−400 cm⁻¹ and 3500−200 cm⁻¹, respectively. A detailed vibrational analysis in terms of assignment of the observed frequencies of this molecule for its four most probable conformations in liquid phase, having symmetries C _s and C _l , has been done using normal co-ordinate calculations. The force-field transferred from already studied lower chain chloro-alkanes is subjected to refinement so as to fit the observed infrared and Raman frequencies with those of calculated ones. The potential energy distribution has also been calculated for each mode of vibration of the molecule for the most probable conformations present in its liquid phase.     

Betulin and its natural resource as potential anticancer drug candidate seen by FT‐Raman and FT‐IR spectroscopy

The Fourier transform Raman and IR spectra of betulin (lup‐20(29)‐ene‐3β,28‐diol) crystalline powder were recorded and analyzed. The vibrational wavenumbers and the corresponding vibrational assignments were theoretically studied using the Gaussian 03 package. The calculated vibrational wavenumbers with the B3LYP density functionals are generally consistent with the observed spectra. A complete vibrational characterization of betulin modes has been proposed here for the first time. Based on the vibrational analysis, two direct applications of the results have been described. It was shown that the outer bark of Betula Pendula Roth (the birch tree) contains betulin as a major component along with minor amounts of betulinic acid (BA), lupeol and other pentacyclic triterpenes derivatives. Since the major disadvantage of betulin is its low solubility, giving rise to serious problems in making pharmaceutical formulations, several guest–host type of complexes of betulin–cyclodextrins have been prepared and analyzed using FT‐Raman spectroscopy. Based on the vibrational analysis, it was concluded that the OH and CH₂OH functional groups are free from chemical interactions with the cyclodextrin cavity. Copyright © 2010 John Wiley & Sons, Ltd.