Line Positions and Intensities of the ν1+ ν2+ 3ν3, ν2+ 4ν3, and 3ν1+ 2ν2Bands of Ozone

Using a Fourier transform spectrometer, we have recorded the spectra of ozone in the region of 4600 cm⁻¹, with a resolution of 0.008 cm⁻¹. The strongest absorption in this region is due to the ν₁+ ν₂+ 3ν₃band which is in Coriolis interaction with the ν₂+ 4ν₃band. We have been able to assign more than 1700 transitions for these two bands. To correctly reproduce the calculation of energy levels, it has been necessary to introduce the (320) state which strongly perturbs the (113) and (014) states through Coriolis- and Fermi-type resonances. Seventy transitions of the 3ν₁+ 2ν₂band have also been observed. The final fit on 926 energy levels withJ_max= 50 andK_max= 16 gives rms = 3.1 × 10⁻³cm⁻¹and provides a satisfactory agreement of calculated and observed upper levels for most of the transitions. The following values for band centers are derived: ν₀(ν₁+ ν₂+ 3ν₃) = 4658.950 cm⁻¹, ν₀(3ν₁+ 2ν₂) = 4643.821 cm⁻¹, and ν₀(ν₂+ 4ν₃) = 4632.888 cm⁻¹. Line intensities have been measured and fitted, leading to the determination of transition moment parameters for the two bands ν₁+ ν₂+ 3ν₃and ν₂+ 4ν₃. Using these parameters we have obtained the following estimations for the integrated band intensities,S_V(ν₁+ ν₂+ 3ν₃) = 8.84 × 10⁻²²,S_V(ν₂+ 4ν₃) = 1.70 × 10⁻²², andS_V(3ν₁+ 2ν₂) = 0.49 × 10⁻²²cm⁻¹/molecule cm⁻²at 296 K, which correspond to a cutoff of 10⁻²⁶cm⁻¹/molecule cm⁻².     

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.     

High resolution infrared spectrum of the ν4 band of DCCF

The bending vibration-rotation band ν₄ of DCCF was studied. The measurements were carried out with a Fourier spectrometer at a resolution of about 0.03 cm^?1. The constants B₀=0.29141(1)cm^?1, α₄=?5.02(2)×10^?4cm^?1, q₄=4.52(3)×10^?4cm^?1, and D₀=9.2(4)×10^?8cm^?1 were derived. The rotational analysis of the “hot” bands 2ν₄(Δ) ← ν₄(II) and 2ν₄(Σ⁺) ← ν₄(II) was performed. In addition, the “hot” bands ν₄ + ν₅ ← ν₅ were assigned. A set of vibrational constants involved was derived.     

Measurements and calculations of Ar-broadening parameters of water vapour transitions in a wide spectral region

The water vapour line-broadening (γ) and shift (δ) coefficients for 310 lines of 10 vibrational bands ν₁, ν₃, 2ν₂, ν₁+ ν₂, ν₂+ ν_3, 2ν₂ +ν₃, 2ν₁, ν₁+ ν₃, 2ν₃ and ν₁ +2ν₂ induced by argon pressure were measured with a Bruker IFS HR 125 spectrometer. The measurements were performed at room temperature, at the spectral resolution of 0.01 cm^–1 and over a wide pressure range of Ar. The calculations of the broadening coefficients γ and δ were performed in the framework of the semi-classical method. The intermolecular potential was taken as the sum of the atom–atom potential and the vibrationally and rotationally dependent isotropic induction+dispersion potential. The measured γ and δ were combined with literature data for the ν₂ and 3ν₁+ν₃, 2ν₁+2ν₂+ν₃ vibrational bands, and the optimal sets of potential parameters that gave the best agreement with the measured broadening coefficients for each vibrational band separately were found. Then, combined experimental data of 13 vibrational bands of H₂O perturbed by Ar were used to determine the analytical dependence of some potential parameters on vibrational quantum numbers.     

Absolute Line Intensities in Acetylene: The 1.5-μm Region

We measured 305 absolute line intensities in the ν₁+ν₃(Σ⁺_u)-0(Σ⁺_g) band of ¹²C₂H₂ and ¹³C¹²CH₂ and the ν₁+ν₂+(ν¹₄+ν⁻¹₅)⁰(Σ⁺_u)-0(Σ⁺_g), ν₁+ν₃+ν¹₄(Π_g)-ν¹₄(Π_g), and ν₁+ν₃+ν₅¹(Π_u)-ν₅¹(Π_u) bands of the main isotopomer, all observed near 1.5 μm. The absolute intensity of these bands are respectively 6.4882 (34), 0.12337 (10), 0.083746 (71), 0.58771 (28), and 0.32126 (11) cm⁻² atm⁻¹ at 296 K. In addition, we also determined Herman-Wallis factors for the first time in this spectral region.     

Oxygen vacancy in LiTiPO5 and LiTi2(PO4)3: A first-principles study

The structures of LiTiPO₅ and LiTi₂(PO₄)₃, as well as the possibility of oxygen vacancies formation in the systems are studied by first-principles calculations. It is found that oxygen vacancies can be formed in LiTiPO₅ and LiTi₂(PO₄)₃ under oxygen poor condition. The formation of oxygen vacancies introduce a defect band within their band gaps, which is expected to improve the electronic conductivity of LiTiPO₅ and LiTi₂(PO₄)₃ significantly. Meanwhile, a great concentration of oxygen vacancies may increase the discharge voltage of LiTiPO₅ and LiTi₂(PO₄)₃.     

XPS and ionic conductivity studies on Li1.3Al0.15Y0.15Ti1.7(PO4)3 ceramics

Li_1.3Al_0.15Y_0.15Ti_1.7(PO₄)₃ compound was synthesized by solid-state reaction, and ceramics were sintered. The surfaces of the ceramics were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. Li_1.3Al_0.15Y_0.15Ti_1.7(PO₄)₃ samples were tested in solid galvanic cells Ag|O₂+CO₂|Li₂CO₃|Li_1.3Al_0.15Y_0.15Ti_1.7(PO₄)₃|LiMnO₂+Mn₂O₃|O₂|Ag. The electromotive force measurements of this cell indicated that investigated samples are practically pure Li-ion conductors. Impedance spectroscopy studies have been performed in the frequency range 10^?2–3·10⁹ Hz and temperatures from ?57 °C to 334 °C. Three dispersion regions related to Li⁺ ionic transport in bulk, grain boundaries of the ceramics and to polarization of electrodes have been found. Total conductivity changes according to Arrhenius law in the studied temperature range, but an anomalous behavior was observed for the bulk conductivity of the ceramics.     

Effect of sintering conditions on the properties of sol-gel-derived Li<Subscript>1.3</Subscript>Al<Subscript>0.3</Subscript>Ti<Subscript>1.7</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

Solid electrolyte Li_1.3Al_0.3Ti_1.7(PO₄)₃ was prepared by sol-gel method under different sintering conditions. The structural identification, surface morphology, electrochemical window, ionic conductivity, and activation energy of the Li_1.3Al_0.3Ti_1.7(PO₄)₃ sintered pellets were investigated by X-ray diffraction, scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. It is found that the sintering temperature and time have considerable effect on the properties of the Li_1.3Al_0.3Ti_1.7(PO₄)₃ sintered pellets. The Li_1.3Al_0.3Ti_1.7(PO₄)₃ pellet sintered at 900 °C for 2 h is denser than the pellets sintered at other conditions. Different sintering conditions result in the sintered pellet with different porosity. However, the sintering conditions have little effect on the electrochemical window of Li_1.3Al_0.3Ti_1.7(PO₄)₃. Among the Li_1.3Al_0.3Ti_1.7(PO₄)₃ pellets sintered at various conditions, the pellet sintered at 900 °C for 2 h shows the highest ionic conductivity of 3.46 × 10⁻⁴ S cm⁻¹ and the lowest activation energy of 0.2821 eV.     

Integral intensities of absorption bands of silicon tetrafluoride in the gas phase and cryogenic solutions: Experiment and calculation

The spectral characteristics of the SiF₄ molecule in the range 3100–700 cm^?1, including the absorption range of the band ν₃, are studied in the gas phase at P = 0.4–7 bar and in solutions in liquefied Ar and Kr. In the cryogenic solutions, the relative intensities of the vibrational bands, including the bands of the isotopically substituted molecules, are determined. The absorption coefficients of the combination bands 2ν₃, ν₃ + ν₁, ν₃ + ν₄, and 3ν₄ are measured in the solution in Kr. In the gas phase of the one-component system at an elevated pressure of SiF₄, the integrated absorption coefficient of the absorption band ν₃ of the ²⁸SiF₄ molecule was measured to be A(ν₃) = 700 ± 30 km/mol. Within the limits of experimental error, this absorption coefficient is consistent with estimates obtained from independent measurements and virtually coincides with the coefficient A(ν₃) = 691 km/mol calculated in this study by the quantum-chemical method MP2(full) with the basis set cc-pVQZ.     

Raman spectroscopic study of the sulfite‐bearing minerals scotlandite,hannebachite and orschallite: implications for the desulfation of soils

The structures of the naturally occurring sulfite‐bearing minerals scotlandite, hannebachite and orschallite have been studied by Raman spectroscopy. Raman bands are observed for scotlandite PbSO₃ at 935, 880, 622 and 474 cm⁻¹ and are assigned to the (SO₃)²⁻ν₁(A₁), ν₃(E), ν₂(A₁) and ν₄(E) vibrational modes, respectively. For hannebachite (CaSO₃)₂·H₂O these bands are observed at 1005, 969 and 655 cm⁻¹ with multiple bands for the ν₄(E) mode at 444, 492 and 520 cm⁻¹. The Raman spectrum of hannebachite is very different from that of the compound CaSO₃·2H₂O. It is proposed, on the basis of Raman spectroscopy, that in the mineral hannebachite, the sulfite anion bonds to Ca through the sulfur atom. The Raman spectrum of the mineral orschallite Ca₃[SO₄](SO₃)₂·12H₂O is complex resulting from the overlap of sulfate and sulfite bands. Raman bands at 1005 cm⁻¹, 1096 and 1215 cm⁻¹ are assigned to the (SO₄)²⁻ν₁ symmetric and ν₃ asymmetric stretching modes. The two Raman bands at 971 and 984 cm⁻¹ are attributed to the (SO₃)²⁻ν₃(E) and ν₁(A₁) stretching vibrations. The formation of sulfite compounds in nature offers a potential mechanism for the removal of sulfates and sulfites from soils. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl carbonate mineral voglite

Raman spectroscopy, complemented with infrared spectroscopy, was used to study the uranyl carbonate mineral voglite. The mineral has the formula Ca₂Cu²⁺ [(UO₂)(CO₃)₃](CO₃)^•6H₂O, and bands attributed to these vibrating units are readily identified in the Raman spectrum. Symmetric stretching modes at 836 and 1094 cm⁻¹ are assigned to ν₁(UO₂)²⁺ and ν₁(CO₃)²⁻ units, respectively. The ν₃ antisymmetric stretching modes of (UO₂)²⁺ are not observed in the Raman spectrum but may be readily observed in the infrared spectrum at 898 cm⁻¹. The ν₃ antisymmetric stretching mode of (CO₃)²⁻ is observed in the Raman spectrum at 1369 cm⁻¹ as a low intensity band as is also the ν₃(CO₃)²⁻ infrared modes at 1362, 1425, 1509 and 1566 cm⁻¹. No ν₂(CO₃)²⁻ Raman bending modes are observed for voglite. The Raman band at 749 cm⁻¹ and the two infrared bands at 747 and 709 cm⁻¹ are assigned to the ν₄(CO₃)²⁻ bending modes. U O bond and O H…O bond lengths in the structure of voglite were inferred from the infrared and Raman spectra. Copyright © 2007 John Wiley & Sons, Ltd.     

High-Resolution Infrared Spectrum of H3SiI in the ν1/ν4Region near 2200 cm

The Fourier transform infrared spectrum of H₃SiI has been recorded in the ν₁/ν₄region from 2075 to 2315 cm⁻¹at an optical resolution of 2.3 × 10⁻³cm⁻¹. The ν₁/ν₄fundamental bands and the (ν₁+ ν₃) − ν₃/(ν₄+ ν₃) − ν₃hot bands have been rotationally investigated. Numerous local perturbations have been observed in the ν₁and ν₄bands and in the hot bands. Without the lines involved in perturbations, more than 2900 transitions of the ν₁/ν₄bands were used to determine the band origins and the vibration–rotation parameters of the ν₁= 1 and νv₄= 1 states. A least-squares fit of 766 apparently unperturbed transitions of the hot bands gave the parameters of the ν₁= ν₃= 1 and ν₄= ν₃= 1 states. Thel(2, 2) resonance in ν₄and theA₁–E Coriolis coupling between ν₁and ν₄have been investigated. Most of the local perturbations have been studied individually using a simple model by which the main perturber for each resonance was identified.     

High-Resolution Infrared Spectra of the OOO Ozone Isotopomer in the Range 900-5000 cm: Line Positions

In pursuing the systematic study of ozone high-resolution infrared spectra, we present here the analysis of line positions of the ¹⁶O¹⁸O¹⁶O isotopomer. The recorded spectra cover the range 900-5000 cm⁻¹, that has allowed 13 bands to be observed: ν₁, ν₃, 2ν₂, ν₂+ν₃, ν₁+ν₂, ν₁+ν₃, ν₁+ν₂+ν₃, 3ν₃, 2ν₁+ν₃, ν₂+3ν₃, ν₁+3ν₃, ν₁+ν₂+3ν₃, and 5ν₃. The analysis of these bands has been performed using effective rovibrational Hamiltonians for 10 polyads of interacting upper vibrational states. To correctly reproduce all observed transitions, it has been necessary to account for resonance perturbations due to “dark” states: (002), (200), (012), (210), (102), (310), (004), (014), (320), (104), and (311). We present the results for spectroscopic parameters (vibrational energy levels, rotational and centrifugal distortion constants, and resonance coupling parameters), as well as the statistics for rovibrational energy levels, range of observed transitions, and typical example of wavefunction mixing coefficients. A comparison of observed band centers with those predicted from an isotopically invariant potential function is discussed. The R.M.S. deviation between predicted and directly observed band centers is ≈0.2 cm⁻¹ up to 2800 cm⁻¹ and ≈0.5 cm⁻¹ for all 13 bands up to 4800 cm⁻¹.     

The Hot Bands of Methane between 5 and 10 μm

Experimental line intensities of 1727 transitions arising from nine hot bands in the pentad–dyad system of methane are fitted to first and second order using the effective dipole moment expansion in the polyad scheme. The observed bands are ν₃− ν₂, ν₃− ν₄, ν₁− ν₂, ν₁− ν₄, 2ν₄− ν₄, ν₂+ ν₄− ν₂, ν₂+ ν₄− ν₄, 2ν₂− ν₂, and 2ν₂− ν₄, and the intensities are obtained from long-path spectra recorded with the Fourier transform spectrometer located at Kitt Peak National Observatory. For the second order model, some of the 27 intensity parameters are not linearly independent, and so two methods (extrapolation and effective parameters) are proposed to model the intensities of the hot bands. In order to obtain stable values for three of these parameters, 1206 dyad (ν₄, ν₂) intensities are refitted simultaneously with the hot band lines. The simultaneous fits to first and second order lead to rms values respectively of 21.5% and 5.0% for the 1727 hot band lines and 6.5% and 3.0% for the 1206 dyad lines. The band intensities of all 10 pentad–dyad hot bands are predicted in units of cm⁻²atm⁻¹at 296 K to range from 0.931 (for 2ν₄− ν₄) to 7.67 × 10⁻⁵(for 2ν₄− ν₂). The total intensities are also estimated to first order for two other hot band systems (octad–pentad and tetradecad–octad) that give rise to weak transitions between 5 and 10 μm.     

FTIR spectrum of vinyl fluoride near 3.6 μm: rovibrational analysis of the ν4+ν7 band and modelling Coriolis resonances in a seven-level polyad

ABSTRACT

The Fourier transform infrared (FTIR) spectrum of vinyl fluoride, H₂C=CHF, has been widely investigated in the region of the ν₄+ν₇ combination band around 2800 cm^?1 at a resolution of 0.005 cm^?1. This vibration of A' symmetry gives rise to an a/b-hybrid band with a predominant a-type component. The rovibrational structure is strongly perturbed and the analysis has been rather complicated since this combination band is involved at least in a seven-level interacting polyad, including the ν₈+2ν₁₀, 2ν₈+ν₁₀, 2ν₇+ν₉, ν₇+ν₈+ν₁₂, ν₅+ν₉+ν₁₀ and ν₇+ν₁₀+ν₁₂ vibrational states. The study has been further complicated by the absence of transitions coming from the perturbers that were considered as dark states. The spectral analysis resulted in the identification of 936 transitions with J" ≤ 46 and K_a" ≤ 11, all belonging to the a-type component. Most of the assigned data have been fitted using the Watson's A-reduction Hamiltonian in the I^r representation and proper Coriolis perturbation operators. The model employed includes seven different resonances within a complex polyad resonant system and a set of spectroscopic constants for the ν₄+ν₇ combination band, for the dark states, and Coriolis coupling coefficients have been determined.     

Analysis of the CH3D Nonad from 2000 to 3300 cm

As part of the simultaneous analysis of line positions and intensities of the first two polyads of monodeuterated methane, the results achieved for the region 3-5 μm are reported. It involves the three highest fundamentals, (ν₁, ν₂, ν₄), overlapped by overtone (2ν₃, 2ν₅, 2ν₆) and combination (ν₃+ν₆, ν₃+ν₅, ν₅+ν₆) bands. The theoretical model was based on the global tensorial model implemented in the MIRS package. Some 10 000 line positions and 2400 line intensities have been modeled to ±0.000 88 cm⁻¹ and ±3.6% respectively, using measurements obtained at 0.0056 and 0.011 cm⁻¹ resolution with the Fourier transform spectrometer at National Solar Observatory located at Kitt Peak. The strongest band in this polyad is ν₄(E) at 3016.7 cm⁻¹ with a strength of 6.3×10⁻¹⁸ cm⁻¹/(molecule cm⁻²) at 296 K; the weakest band is 2ν₃(E) at 2597.7 cm⁻¹ with a strength of 1.9×10⁻²⁰ cm⁻¹/(molecule cm⁻²) at 296 K. The total calculated absorption arising from the CH₃D nonad is 8.95×10⁻¹⁸ cm⁻¹/(molecule cm⁻²) at 296 K.     

Anharmonic resonance interactions in the bending manifold associated with ν3 in 13C2D2 studied by high—resolution infrared and Raman spectroscopy

The Q branch of the 2ν₂ ← ν₂ band of ¹³C₂D₂ has been recorded with an instrumental resolution of about 0.003 cm^?1 using inverse Raman spectroscopy combined with stimulated Raman pumping in order to populate the ν₂=1 state. A weak local perturbation evident in the spectrum has been attributed to the effect of an anharmonic resonance between the ν₂=2 and ν₃=ν₄=ν₅=1 Σ⁺ _g, states. To study this interaction, the components of the latter vibrational manifold (Σ⁺ _g, ^? _g and Δ_g), together with all the bending states up to (ν₄ + ν₅)=2 associated with ν₃=1, have been characterized through the analysis of their infrared spectra. Both cold and hot bands from states thermally populated at room temperature, ν₄, ν₅, 2ν₄, 2ν₅ and ν₄ + ν₅, have been recorded in the region between 2300 and 3000 cm^?1 at an effective resolution of about 0.009 cm^?1. A simultaneous analysis of all the assigned transitions has been performed on the basis of a theoretical model which takes into account the rotational and vibrational ?-type resonances within each vibrational manifold, the Darling-Dennison anharmonic resonance between the ν₃ + 2ν₄ and ν₃ + 2ν₅ states, and the anharmonic interaction between the 2ν₂ and ν₃ + ν₄ + ν₅ states.     

Natural halotrichites—an EDX and Raman spectroscopic study

Raman spectroscopy has been used to characterise four natural halotrichites: halotrichite FeSO₄.Al₂(SO₄)₃. 22H₂O, apjohnite MnSO₄.Al₂(SO₄)₃.22H₂O, pickingerite MgSO₄.Al₂(SO₄)₃.22H₂O and wupatkiite CoSO₄.Al₂(SO₄)₃.22H₂O. A comparison of the Raman spectra is made with the spectra of the equivalent synthetic pseudo‐alums. Energy dispersive X‐ray analysis (EDX) was used to determine the exact composition of the minerals. The Raman spectrum of apjohnite and halotrichite display intense symmetric bands at ∼985 cm⁻¹ assigned to the ν₁(SO₄)²⁻ symmetric stretching mode. For pickingerite and wupatkiite, an intense band at ∼995 cm⁻¹ is observed. A second band is observed for these minerals at 976 cm⁻¹ attributed to a water librational mode The series of bands for apjohnite at 1104, 1078 and 1054 cm⁻¹, for halotrichite at 1106, 1072 and 1049 cm⁻¹, for pickingerite at 1106, 1070 and 1049 cm⁻¹ and for wupatkiite at 1106, 1075 and 1049 cm⁻¹ are attributed to the ν₃(SO₄)²⁻ antisymmetric stretching modes of ν₃(B_g) SO₄. Raman bands at around 474, 460 and 423 cm⁻¹ are attributed to the ν₂(A_g) SO₄ mode. The band at 618 cm⁻¹ is assigned to the ν₄(B_g) SO₄ mode. The splitting of the ν₂, ν₃ and ν₄ modes is attributed to the reduction of symmetry of the SO₄ and it is proposed that the sulphate coordinates to water in the hydrated aluminium in bidentate chelation. Copyright © 2007 John Wiley & Sons, Ltd.     

Isotope effects in the vibrational spectrum of the SF<Subscript>6</Subscript> molecule

The IR absorption spectra of solutions of SF₆ in liquid argon are studied at a temperature of 93 K in the concentration interval 10^?5–10^?7 mole fractions. A sample with a natural abundance of isotopes and a monoisotope ³⁴SF₆ sample are studied. The frequencies, half-widths, and relative intensities of bands in the vibrational spectrum of all isotopomers of the molecule are determined. For the ³⁴SF₆ molecule, the ratio of integral absorption coefficients of fundamental bands A(ν₄)/A(ν₃)=0.07(6) is larger than ³²SF₆:A(ν₄)/A(ν₃)=0.66(4) for the ³²SF₆ molecule, which corresponds to the same signs of P′₃ and P′₄. The change in the intensity of the ν₂+ν₆ and ν₅+ν₆ bands upon isotopic substitution is explained by the change in the resonance contributions of due to the isotope shift of the ν₃ band.