Study on Infrared Spectral Radiance by Remote Fourier Transform Infrared Spectroscopy

Abstract

Infrared emission spectra emitted by high luminosity infrared pyrotechnics have been observed remotely using the Fourier transform infrared spectroscopy. The primary purpose of the study is to determine infrared spectral radiance distribution, their time—resolved spectra and integrated emission energy. The spectra have been recorded between 4000 – 800cm^?1 region with spectral resolution of 4cm^?1. The study is very important for many applications.     

Optimization of soft x-ray line emission from laser-produced carbon plasma with laser intensity

Absolute measurement for He-α resonance (1s^{2 1}S₀?1s2p¹ P ₁, at 40.2 Å) line emission from a laser-produced carbon plasma has been studied as a function of laser intensity. The optimum laser intensity is found to be ≈1.3×10¹² W/cm² for the maximum emission of 3.2 × 10¹³ photons sr^?1 pulse^?1. Since this line lies in the water window spectral region, it has potential application in x-ray microscopic imaging of biological sample in wet condition. Theoretical calculation using corona model for the emission of this line is also carried out with appropriate ionization and radiative recombination rate coefficients     

Computer Resolution and Franck-Condon Analysis of the Electronic Absorption Spectrum of KMnO4 in Water

Abstract

The electronic absorptíon spectrum of KMnO₄ in water solution was analyzed. The spectral contour was resolved into component bands and then Franck-Condon approach was applied. In the investigated range of 13000–48000 cm^?1 a presence of three structureless and of two vibronic strong bands was stated. The change in the Mn-O equilibrium bond length was found to be 10.5pm for 2e·1t₁ transition (vibronic band about 18000cm^?1) and to be 16pm for the 2e·3t₂ transition (vibronic band about. 30000cm_?1). The appropriate wavenumber of the vibrational mode in these excited electronic states was found to be 735cm^?1 and about 780cm^?1, respectively. The ground electronic state wavenumber of the totally symmetric vibrational mode was fitted to be equal to 828cm^?1. Details of the proposed method of computer elaboration of electronic spectra with vibrational structure were discussed.

Electronic absorption spectra of some inorganic comppunds consist of a number of strongly overlapped bands due to their vibronic structure.^1–5 A detailed analysis of spectral contours of such compounds provides some useful information about their structure in both ground excited electronic states.

The electronic spectrum of permanganate ion is the typical example of vibronic spectra.¹ The main part of the past works based on the analysis of permanganate ion spectra in low temperatures and different polarizations. In such conditions the vibronic structure is rather good resolved and can be effectively studies.^1,3,6 Spectra of solutions as a rule are relatively poor resolved so their analysis has to be more sophisticated.

The main purpose of this work is a presentation of a new computer method for an effective study of vibronic spectra of solutions. This method has been applied to the electronic absorption spectrum of KMnO₄ in water. The method allowed us to fit the geometric parameters of spectral contour, to establish the origins and parameters of two progressions in the UV/VIS range as well as to calculate the changes in the Mn-0 equilibrium bond lengths and vibrational energy resulting from the electronic excitations of the soluted permanganate ion.     

Vibrational spectroscopic characterization of the magnesium borate-phosphate mineral lüneburgite

ABSTRACT

Lüneburgite, a rare magnesium borate-phosphate mineral from Mejillones, Chile, has been characterized using Raman and mid-infrared spectroscopy methods. Boron tetrahedra are characterized by sharp Raman band at 877?cm^?1, attributed to the ν₁[BO₄]^5? symmetric stretching mode. The phosphate anion is associated with a distinct band at 1032?cm^?1, attributed to the ν₃[PO₄]^3? antisymmetric stretching mode. The most intensive Raman band at 734?cm^?1 is ascribed to stretching vibrations of bridging oxygen atoms in boron–oxygen–phosphor bridges. Bonds associated with water bending mode and stretching vibration are observed at 1661?cm^?1 (infrared) and in the 3000–3500?cm^?1 region (Raman and infrared spectrum).     

The submillimeter-wave spectrum and spectroscopic constants of SO2 in the ground state

The submillimeter-wave spectrum of SO₂ has been recorded with 0.004 cm^?1 resolution in the region 8–90 cm^?1. About 2000 lines were observed, 1500 of which have been assigned to the ground state rotational transitions of ³²SO₂. Molecular constants up to the 10th order have been derived, combining our data with the available microwave data in the literature. SO₂ rotational spectrum line positions up to 90 cm^?1 can be reproduced from these constants, within the experimental accuracy (2 × 10^?4 cm^?1).     

New assignments in the submillimeter emission spectrum of the stratosphere

New line assignments in the spectrum of the stratospheric submillimeter emission, measured with unapodized resolution of 0.0033 cm^–1, have been made. Positive evidence for the presence of symmetric and asymmetric ozone isotopes, water vapour excited to the (010) level, and HCN is given.     

Calibration of the R ruby fluorescence lines in the pressure range [0-1 GPa] and the temperature range [250-300 K]

Abstract

The pressure range [&1 GPa] and the temperature range [250–300 K] are commonly used in many science fields like biology, agro-chemistry, pharmacology, or geology. In this paper, the calibration of the ruby R lines of fluorescence is performed in these pressure and temperature ranges, using the melting curve of pure water. The linear shifts of ruby peaks are equal to ?0.140cm^?1/K and ?0.768cm^?1/kbar with R₁, and to ?0.137cm^?1/K and ?0.779 cm^?1/kbar with R₂. The accuracy of pressure measurements can be as good as ± 10MPa if the temperature is known with ±0.5 K. Such a precision is achieved if: (1) the position of each peak is determined using an inversion method; (2) daily shifts of the spectrometer are corrected before each acquisition; (3) peak positions of each ruby are known at ambient pressure and temperature.     

Extracting molecular potentials from incomplete spectroscopic information

We extend our recently developed inversion method to extract excited-state potentials from fluorescence line positions and line strengths. We consider a previous limitation of the method arising due to insufficient input data in cases where the relatively weaker emission data are not experimentally available. We develop a solution to this problem by ‘regenerating’ these weak transition lines via applying a model potential, e.g. a Morse potential. The result of this procedure, illustrated for the Q-branch emission from the lowest three vibrational levels of the B(¹Π) state of LiRb, is shown to have an error of 0.29 cm^?1 in the classically allowed region and a global error of 5.67 cm^?1 for V ≤ E(ν′ = 10). The robustness of this procedure is also demonstrated by considering the statistical error in the measured line intensities.     

Line strength and collisional broadening coefficients of H2O at 2.7 μm for natural gas quality assurance applications

We employed tunable diode laser absorption spectroscopy to measure the line strength, the methane (CH₄), ethane (C₂H₆) and the propane (C₃H₈) broadening coefficients for the 523–422 H₂O transition at 3619.61 cm^?1. Water amount fractions generated by a stable and accurate humidity transfer standard, traceable to the SI units via the German national humidity standard, were used to calibrate the spectroscopic line strength measurements. We focus on the traceability of the measured line data to the SI and on uncertainty assessments following the guidelines of the Guide to the Expression of Uncertainty in Measurement. We determined the line strength to be (8.42 ± 0.07)×10^?20 cm^?1/(cm^?2 molecule) corresponding to a relative uncertainty of ±0.8%. To the best of our knowledge, we report the first methane, ethane and propane broadening coefficients of (8.037 ± 0.056)×10^?5 cm^?1/hPa, (9.077 ± 0.064)×10^?5 cm^?1/hPa and (10.469 ± 0.073)×10^?5 cm^?1/hPa for the 523–422 H₂O transition at 3619.61 cm^?1, respectively. The relative combined uncertainties of the stated CH₄, C₂H₆ and C₃H₈ broadening coefficients are in the ±0.7% range.     

Hard mode infrared spectroscopy of CaTiO3—CaFeO2.5 perovskites

Abstract

Powder-absorption infrared (IR) spectra of perovskites CaFe_xTi_1?x O_3?x/2 (0≤x≤1) annealed at different temperatures were investigated at room temperature in the range 135–2000 cm^?1. The spectra change as a function of composition, annealing temperature and structural state (order-disorder of oxygen vacancies). Autocorrelation analysis has been used to determine variations of average line widths of groups of peaks in the primary IR spectra. The band widths increase on increasing Fe content in the region of the structures with disordered oxygen vacancies and they decrease on going through the order-disorder boundary. High degrees of local structural heterogeneity are suggested by the effective line widths of the phases at intermediate compositions. The intensity of bands at ～150 and ～443 cm^?1 decreases with increasing Fe content in the compositional range of the disordered structures. Finally, for every annealing temperature, the frequency of the band at ～600cm^?1 systematically shifts to higher values on increasing Fe content, these values decreasing again for the fully ordered structures.     

The Electronic Absorption Spectrum of Hafnium Monochloride

Abstract

Intracavity laser spectroscopy has been applied for investigation of absorption spectrum of HfCl molecule. In the region 560–700 nm 59 bands have been obtained. Rotational structure analysis of 0–0 band indicated that Hund's case (c) of angular moment coupling applied to this molecule. The molecular constants (cm^?1) calculated for upper and ground electronic states are: ω′ = 353.05 cm^?1, ω″ = 379.65 cm^?1, B′=0.21486 cm^?1 B″ = 0.21801 cm^?1.     

Anti-stokes emission in an additively colored KCl caused by excitation with a Nd: YAG laser

Abstract

We have observed the quadratic laser power dependence of two anti-Stokes emission bands at 15100cm^?1 and 14000cm^?1 in an additively colored KCl when excited with a Nd:YAG laser. The cross section of two photon absorption to cause the 14000cm^?1 band is estimated to be 4×10^?40cm⁴sec. We have observed that emission intensities are dependent on temperature in the range between 4. 2K and 130K. They are enhanced by means of optical bleaching and also with the increase of the F concentration. From a qualitative analysis of these observations, we propose that these emissions are correlated to the loose aggregation of the F centers.     

High resolution pure rotational spectrum of water vapor enriched by H217O and H218O

The pure rotational spectrum of a mixture of H₂¹⁶O, H₂¹⁷O and H₂¹⁸O between 50 and 730 cm^?1 was recorded on the Fourier transform spectrometer at the University of Oulu. The resolution achieved was about 0.010 cm^?1 and the precision of the unblended lines was better than 0.001 cm^?1. About 1100 lines were assigned. The measured line positions of H₂¹⁷O and H₂¹⁸O were compared with the values derived from the rotation and distortion constants given in the literature.     

Effect of changes of the HITRAN database on transmittance calculations in the near-infrared region

In order to retrieve from high spectral resolution measurements with high accuracy, it is necessary to be able to evaluate the transmittance precisely. However, the uncertainty of the spectroscopic parameters is one of the most important contributions that affect the accuracy of transmittance. HITRAN is a compilation of spectroscopic parameters which has been updated several times. The transmittance calculations using the line parameters from the HITRAN’2000 database and the HITRAN’2004 database have been compared over the near infrared range from 4200 to 10,000 cm^?1. The differences between calculated transmittances over this spectral range are mainly caused by changes of the line parameters for H₂O, CO₂ and CH₄. For the tropical atmosphere, the differences are very prominent. Transmittance calculations for the sub-arctic winter atmosphere are less sensitive to the changes in the HITRAN database than those for the tropical atmosphere; but, the changes of line parameters still can not be ignored when considering the relative differences. For example, the relative difference is ～35% at 5073.3 cm^?1 with 0.2 cm^?1 spectral resolution. The comparisons have shown that it is important to pay attention to the changes of line parameters of the HITRAN database or to use the latest edition so as to improve the accuracy of atmospheric sounding with high spectral resolution.     

Comparison of band model and integrated line-by-line synthetic spectra for methane in the 2.3 μm region

The 2.3 μm spectral region of methane can be used to retrieve cloud properties of planetary spectra, provided parameters for the methane spectrum are known. Two standard techniques for calculating absorption spectra in this region are compared here. A Voigt profile Mayer-Goody random band model is applied, using coefficients empirically fitted by Fink et al. to CH₄ spectra recorded with high absorping amounts at 10 cm^?1 resolution. Calculation of the absorption is also done with a line-by-line direct integration method for the same gas conditions using molecular parameters obtained by combining an older unpublished list of observed positions and estimated line strengths (derived from 0.04 cm^?1 resolution data) with quantum assignments from the literature. The molecular parameters have been evaluated for the 4180–4590 cm^?1 region by comparing new laboratory spectra with 0.01 cm^?1 resolution recorded at 296 and 153K with synthetic spectra calculated at the same conditions. The deficiencies of the molecular parameters and random band coefficients for this spectral region of CH₄ are then discussed qualitatively and demonstrated by comparing 10 cm^?1 resolution synthetic spectra calculated by both methods for the same gas conditions at 296, 153, and 55 K.Curves of growth of the total equivalent width are calculated at 296 and 55K for a pathlength of 50 cm and pressures up to 10 atm. Changing the mean line spacing in the band model gives better agreement between the spectra calculated by the two techniques at low gas temperatures. The required multiplier has been determined for the mean line spacing for pressures from 10^?6 to 10^?1 atm at 55, 100, and 150 K.     

17O12C17O and 18O12C17O spectroscopy in the 1.6 μm region

Near infrared spectra of a carbon dioxide sample enriched with oxygen-17 have been recorded using a high-resolution continuous scan Fourier transform interferometer fitted with a femto OPO/Idler laser source. Cavity enhanced absorption has been achieved in a static gas cell allowing an optimal rms noise equivalent absorption of 1.2?×?10^?10?cm^?1?Hz^?1/2 per spectral element to be reached, corresponding to α_min?=?10^?8?cm^?1. Spectra were calibrated against acetylene reference line positions. Three bands in the 3ν₁?+?ν₃ tetrad in both ¹²C¹⁷O₂ and ¹²C¹⁷O¹⁸O have been identified and rotationally analyzed, as well as some related hot bands, eight of which are newly reported and three with their analysis updated compared with a preliminary report (X. de Ghellinck d’Elseghem Vaernewijck et al., Chem. Phys. Lett. 514, 29 (2011)).     

Vibrational Spectroscopy of the Borate Mineral Priceite—Implications for the Molecular Structure

ABSTRACT

Priceite is a calcium borate mineral and occurs as white crystals in the monoclinic pyramidal crystal system. We have used a combination of Raman spectroscopy with complimentary infrared spectroscopy and scanning electron microscopy with Energy-dispersive X-ray Spectroscopy (EDS) to study the mineral priceite. Chemical analysis shows a pure phase consisting of B and Ca only. Raman bands at 956, 974, 991, and 1019 cm^?1 are assigned to the BO stretching vibration of the B₁₀O₁₉ units. Raman bands at 1071, 1100, 1127, 1169, and 1211 cm^?1 are attributed to the BOH in-plane bending modes. The intense infrared band at 805 cm^?1 is assigned to the trigonal borate stretching modes. The Raman band at 674 cm^?1 together with bands at 689, 697, 736, and 602 cm^?1 are assigned to the trigonal and tetrahedral borate bending modes. Raman spectroscopy in the hydroxyl stretching region shows a series of bands with intense Raman band at 3555 cm^?1 with a distinct shoulder at 3568 cm^?1. Other bands in this spectral region are found at 3221, 3385, 3404, 3496, and 3510 cm^?1. All of these bands are assigned to water stretching vibrations. The observation of multiple bands supports the concept of water being in different molecular environments in the structure of priceite. The molecular structure of a natural priceite has been assessed using vibrational spectroscopy.     

The far-infrared spectrum of deuterated hydrogen sulfide: The ground state rotational constants of D232S,D234S,HD32S,and HD34S

Pure rotation spectra of deuterated samples of hydrogen sulfide have been recorded between 25 and 280 cm^?1 with a Fourier transform spectrometer at an apodized resolution of 0.004 cm^?1. Accurate rotational and centrifugal distortion constants have been derived from the observed line positions for the four isotopic species D₂³²S, D₂³⁴S, HD³²S, and HD³⁴S. Finally, an extensive list of calculated and observed line positions, together with their calculated intensities is presented.     

A simultaneous analysis of the microwave,submillimeterwave, far infrared,and infrared-microwave two-photon transitions between the ground and ν2 inversion-rotation levels of 14NH3

Fourier transform infrared spectra of the inversion-rotation transitions have been measured with 0.010-cm^?1 resolution between 40 and 300 cm^?1 in the ground state and ν₂ excited states of ¹⁴NH₃. Submillimeterwave spectra of the inversion and inversion-rotation transitions in the ν₂ state of ¹⁴NH₃, including a few Δk = ±3 “perturbation-allowed” transitions, have been measured with microwave accuracy between 540 and 770 GHz. A simultaneous least-squares analysis of these data, the microwave ground-state transition frequencies, and the ν₂ infrared-microwave two-photon transition frequencies has been carried out. A theory of the Δk = ±3n interactions in the ground and ν₂ excited states of ammonia (S. P. Belov, L. I. Gershtein, A. F. Krupnov, A. V. Maslovskij, ?. Urban, V. ?pirko, and D. Papou?ek, J. Mol. Spectrosc.84, 288–304 (1980)) has been used in the analysis. A set of the ground- and ν₂-state molecular parameters has been obtained which describes the experimental data within the precision of the experiment. The “smoothed” values of transition frequencies can be used for calibration purposes with a precision better than 3 × 10^?5 cm^?1 in the submillimeterwave region, better than 10^?3 cm^?1 in the far-infrared region, and better than 1.5 × 10^?3 cm^?1 in the region 700 – 1200 cm^?1.     

Temperature Effects in the Raman Spectrum of Solid Orthocarborane

Abstract

Variable temperature studies of the laser Raman spectrum of solid orthocarborane indicate a change in the line widths of the peaks in the observed frequency region from 745 cm^?1 to 815 cm^?1. A marked change in the line width of the 807 cm^?1 peak around 4°C confirms recently observed anomalies in the NMR spectrum at this temperature.