Rotational spectroscopy of the first excited state of the acetylenic C-H stretch of 3-fluoropropyne performed by infrared-Fourier transform microwave-microwave triple-resonance spectroscopy

The rotational spectra of 3-fluoropropyne in the ground and first excited acetylenic C-H stretch vibrational state have been measured. The pure rotational spectrum of the normal species and the ¹³C isotopomers were measured using FTMW-cwMW double-resonance spectroscopy based on the Autler-Townes (AC Stark) effect. The lineshape properties of this measurement make it possible to determine the transition strength, ΔJ-selection rules, and the relative energy ordering of the quantum states. The frequency accuracy of this technique is tested against a previous pure rotational study of 3-fluoropropyne. The rotational spectrum of vibrationally excited state was obtained through IR-FTMW-cwMW methods. In this technique a single-longitudinal-mode pulsed infrared laser source vibrationally excites the acetylenic C-H stretch with J-selectivity. The rotational spectrum of the excited state is then obtained by FTMW and FTMW-cwMW double-resonance methods. The excited-state measurements have a signal-to-noise ratio comparable to the pure rotational spectrum. The residuals in the excited-state fit are larger than those obtained in the ground-state fit. This greater deviation from a standard asymmetric top spectrum is most likely due to weak perturbations to the acetylenic C-H spectrum.     

High-Resolution Fourier Transform Infrared Spectrum of the ν1+ν3 Band System of HCCH

A high-resolution vibration-rotation overtone spectrum of H¹³C¹²CH has been recorded with a Fourier transform infrared spectrometer in the wavenumber region 6400 to 6700 cm⁻¹. The main band, assigned as the C-H stretching combination band ν₁+ν₃, and some overtone and hot bands have been rotationally analyzed. Altogether eight parallel bands have been observed. The vibrational labels have been deduced on the basis of the assignments of the fundamental ν₃ antisymmetric C-H stretching band system.     

High resolution rovibrational spectroscopy of pyrimidine: Analysis of the B1 modes ν10b and ν4 and B2 mode ν6b

We report the first high resolution rovibrational analysis of the infrared spectrum of pyrimidine (C₄H₄N₂) based on measurements using our Fourier transform spectrometer, the Bruker IFS 125 HR Zürich Prototype (ZP) 2001. Measurements were conducted at room temperature in a White-type cell with effective optical path lengths between 3.2 and 9.6 m and with resolutions ranging from 0.0008 to 0.0018 cm⁻¹ in the region between 600 and 1000 cm⁻¹. The spectrum was analyzed in the ν₄ (), ν_10b () and ν_6b regions of pyrimidine () using an effective Hamiltonian. A total of about 15 000 rovibrational transitions were assigned. The root mean square deviations of the fitted data are in the ranges d_rms = 0.00018-0.00024 cm⁻¹, indicating an excellent agreement of experimental line data with the calculations. The results are discussed briefly in relation to possible extensions to spectra of DNA bases and to intramolecular vibrational redistribution at higher energy. The analysis of the ν_10b and ν₄ bands will also be useful in the interstellar search for pyrimidine in the infrared region.     

The υ1 fundamental bands of trans- and cis-DONO studied by high-resolution Fourier-transform spectroscopy

The absorption spectrum of deuterated nitrous acid DONO in the region from 2350 to 3000 cm⁻¹ has been recorded at a resolution of 0.003 cm⁻¹ using a Fourier-transform spectrometer. For the first time, 1366 a- and b-type transitions in the υ₁ fundamental band of trans-DONO and 741 b-type transitions in the υ₁ fundamental band of cis-DONO have been assigned. Rotational and centrifugal distortion constants up to sextic order were determined for the v₁ = 1 states of trans- and cis-DONO using non-linear least-squares calculations. Synthetic spectra calculated using the new rovibrational constants obtained for both species reproduce the observed spectra very well. In addition, the infrared transitions of this study were used, together with previously published pure rotational transitions, to determine improved rotational and centrifugal distortion constants of the ground states of trans- and cis-DONO.     

Nitrogen-broadened halfwidths of HF lines in the 1-0 band

Nitrogen-broadened halfwidths for seven lines in the fundamental infrared band of HF have been determined from laboratory measurements at room temperature. The spectra were recorded using a Fourier transform spectrometer with a nominal resolution of 0.0603 cm^?1. A nonlinear least-squares spectral-fitting technique was used in the data analysis to obtain halfwidth values for the P3 through R3 lines, with an average uncertainty of approximately 15%.     

Vibrational spectroscopy of perfluoropropionic acid in the region between 1000 and 11 000 cm

Fully fluorinated compounds, known as perfluorinated compounds, are widely used in industrial applications. Recently, some perfluorinated acids have been detected in the atmosphere and the tissues of animals. Some perfluorocarboxylic acids are emitted to the atmosphere from the thermolysis of fluoropolymers and the degradation of fluorotelomer alcohols. The gas phase vibrational spectrum of a representative perfluorocarboxylic acid in the region between 1000 and 11 000 cm⁻¹ has been investigated, with emphasis on the vibrational overtone spectrum in the near-IR region. The most intense transition in the fundamental spectrum is the CF₃ stretch while in the overtone region, the O-H stretch carries most of the intensity. A comparison of the perfluorocarboxylic acid vibrational spectrum with the hydrocarbon analog acid is discussed.     

The NEMESIS planetary atmosphere radiative transfer and retrieval tool

With the exception of in situ atmospheric probes, the most useful way to study the atmospheres of other planets is to observe their electromagnetic spectra through remote observations, either from ground-based telescopes or from spacecraft. Atmospheric properties most consistent with these observed spectra are then derived with retrieval models. All retrieval models attempt to extract the maximum amount of atmospheric information from finite sets of data, but while the problem to be solved is fundamentally the same for any planetary atmosphere, until now all such models have been assembled ad hoc to address data from individual missions.In this paper, we describe a new general-purpose retrieval model, Non-linear Optimal Estimator for MultivariatE Spectral analySIS (NEMESIS), which was originally developed to interpret observations of Saturn and Titan from the composite infrared spectrometer on board the NASA Cassini spacecraft. NEMESIS has been constructed to be generally applicable to any planetary atmosphere and can be applied from the visible/near-infrared right out to microwave wavelengths, modelling both reflected sunlight and thermal emission in either scattering or non-scattering conditions. NEMESIS has now been successfully applied to the analysis of data from many planetary missions and also ground-based observations.     

Dual-beam laser heterodyne spectrometer: Ethylene absorption spectrum in the 10 μm range

A laser heterodyne spectrometer for the 10 m region has been built. A 5 MHz apparatus function is obtained. The improvement of this spectrometer using a dual-beam technique is described. The folding effects in heterodyne spectroscopy are discussed. The recorded lineshapes are explained. An ethylene spectrum is shown as an example.     

Room temperature chirped-pulse Fourier transform microwave spectroscopy of anisole

The room-temperature rotational spectrum of anisole from 8.7 to 18.3 GHz was collected with a waveguide-based chirped-pulse Fourier transform microwave spectrometer whose operating principles are described. Three spectra were assigned, corresponding to the vibrational ground state and the first and second excited states of the lowest frequency torsional mode. Results for the ground state and first excited state are in agreement with prior millimeter wave studies of this molecule. Microwave–microwave double resonance measurements also confirm these assignments.     

The C–D Stretch of Monodeuterated Propargyl Radical (CH2CCD)

The high-resolution infrared spectrum of the monodeuterated propargyl radical (CH₂CCD) has been obtained in the region of its acetylenic C–D stretch. Lower state rotational constants were determined for the molecule. The upper state was significantly perturbed making the upper state rotational constants determined much more uncertain.     

The ν7, ν8, and ν11 bands of propynal, C2HCHO, in the 650 cm region

The infrared spectrum of propynal, C₂HCHO, is studied at high resolution (0.003 cm⁻¹) in the range 570-640 cm⁻¹. The relatively intense ν₁₁ (CC-H out-of-plane bend, 693 cm⁻¹) and ν₇ (CC-H in-plane bend, 651 cm⁻¹) fundamental bands are linked by a strong a-type Coriolis interaction. The somewhat weaker ν₈ (CCO in-plane bend, 614 cm⁻¹) fundamental has a significant Fermi-type interaction with the “dark” background state 3ν₉ (∼618 cm⁻¹). About 1400 lines are assigned and analyzed in terms of a four-state fit in order to obtain accurate band origins, rotational and centrifugal distortion parameters, and Fermi and Coriolis interaction parameters. This represents the first systematic high-resolution infrared study of propynal.     

Photoelektronenspektren organischer verbindungen: III. Photoelektronenspektren acetylensubstituierter kleiner ringe

The high resolution He I photoelectron spectra of vinylacetylene, cyclopropylacetylene, cyclobutylacetylene and cyclohexylacetylene are reported and ionization potentials in the low-binding region are assigned by correlating the spectra with spectra of reference compounds, by using the information supplied by vibrational analysis and by comparing the assignment with the results of MINDO/2 calculations. The resonance integrals β_RS between the π type orbitals of the acetylene moiety (R) and the π and Walsh type orbitals of the substituents (S) are determined by means of a LCMO model, parametrized with spectra of known assignment. The interaction terms H_Rs of cyclopropylacetylene, which are 1.3 eV in the bisected conformation and 0.7 eV in the perpendicular conformation, can be considered as experimental verification of the correlation diagram for vinylcyclopropane given by Hoffmann et al. and provide an explanation of the stability of the gauche conformation of vinylcyclopropane. In the case of cyclobutylacetylene, only estimated values of the interaction term H_RS can be obtained from the spectrum.     

基于太赫兹光谱的氨基酸检测

太赫兹是指频率从0.1到2.0 THz之间的远红外波。与傅里叶红外相比,太赫兹时域光谱能量低,信躁比高,并且无辐射损伤。氨基酸分子的低频振动模式(扭转,集体振动模式和氢键)处在 THz波段。氨基酸是一类重要的生物分子,是组成蛋白质最基本的物质。氨基酸分子以分子间氢键相互连接构成晶体。氨基酸在THz波段比在红外波段体现更多独特吸收特征。到目前为止,已经获得了20种氨基酸分子的太赫兹吸收谱,包括利用太赫兹技术对部分氨基酸的定量分析。氨基酸的太赫兹光谱研究,有利于深层次理解蛋白质/ DNA的低频振动模式及相关生物反应和活性。文章综述了20种氨基酸分子的太赫兹吸收光谱并建立了吸收光谱数据库。总结了太赫兹技术在氨基酸应用方面存在的问题,并对未来发展方向进行展望。     

Electrodynamic response of Ca<Subscript>1 – <Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>TiO<Subscript>3</Subscript> two-phase solid solution in a wide frequency range

The dielectric response of Ca_1–x Pb _x TiO₃ two-phase ceramics is studied in a wide frequency range, from 120 Hz to 100 THz, using impedancemetric radio-frequency methods and infrared spectroscopy. The problems of applications of various dispersion models to analyze infrared spectra of disordered ceramics in which high permittivities are formed in the microwave–terahertz ranges are discussed. The effect of low-frequency relaxation processes on the infrared spectrum and the formation of the constant level of dielectric losses is indicated.     

Vibrational Spectroscopic Investigation,First Hyper Polarizability and Homo–Lumo Analysis of Tetrahydroxy-1,4Quinone Hydrate Using Density Functional Theory and Hartree-Fock Method

The FTIR and FT-Raman spectra of tetrahydroxy-1,4quinone hydrate have been recorded in the regions 4000–400 and 3500–50 cm^–1 respectively. Using the observed Fourier-transform infrared spectroscopy (FTIR) and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound has been carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by the density functional theory (DFT/B3LYP) and Hartree–Fock (HF) method with 6-311+G(d,p) basis set. The difference between the observed and scaled wavenumber values of most of the fundamental vibrations is very small. A detailed interpretation of the infrared and Raman spectra of tetrahydroxy-1,4quinone hydrate is also reported. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule.     

Temperature-dependent absorption cross-sections of HCFC-142b

Following the recent detection of HCFC-142b (1-chloro-1,1-difluoroethane) from space, laboratory infrared absorption cross-section spectra of this molecule in a pure vapour phase have been recorded in the spectral region using Fourier transform spectroscopy. The spectra have been recorded at a resolution of and a range of temperatures from 223 to 283 K. The resulting data show good agreement with the harmonic frequencies and intensities calculated using density functional theory as well as with the integrated absorption intensities of the spectral bands available in the literature. The new cross-sections will allow more accurate retrieval of atmospheric HCFC-142b concentrations using infrared spectroscopic techniques.     

Vibrational spectroscopy characterization of magnetron sputtered silicon oxide and silicon oxynitride films

Vibrational (infrared and Raman) spectroscopy has been used to characterize SiO_xN_y and SiO_x films prepared by magnetron sputtering on steel and silicon substrates. Interference bands in the infrared reflectivity measurements provided the film thickness and the dielectric function of the films. Vibrational modes bands were obtained both from infrared and Raman spectra providing useful information on the bonding structure and the microstructure (formation of nano-voids in some coatings) for these amorphous (or nanocrystalline) coatings. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) analysis have also been carried out to determine the composition and texture of the films, and to correlate these data with the vibrational spectroscopy studies. The angular dependence of the reflectivity spectra provides the dispersion of vibrational and interference polaritons modes, what allows to separate these two types of bands especially in the frequency regions where overlaps/resonances occurred. Finally the attenuated total reflection Fourier transform infrared measurements have been also carried out demonstrating the feasibility and high sensitivity of the technique. Comparison of the spectra of the SiO_xN_y films prepared in various conditions demonstrates how films can be prepared from pure silicon oxide to silicon oxynitride with reduced oxygen content.     

The ν5 band of CH3CH3: High resolution stimulated Raman spectrum and global three band analysis

Rotationally resolved spectrum of ¹²CH₃¹³CH₃ in the region of ν₅ vibrational fundamental (CC stretch) was observed using stimulated Raman spectroscopy. This spectrum was analyzed with data from the ν₁₂ fundamental and transitions from the ν₆, 2ν₆-ν₆, and 3ν₆ torsional bands using a 3-state fit. One torsional component of the ν₅ fundamental is perturbed, interacting with its partner in the ν₆=4 of the torsional stack of the ground vibrational state. As for normal ethane, the coupling was successfully modeled using a Fermi-type interaction. The results mirror that of ¹²CH₃¹²CH₃ in that the inclusion of the Fermi-type interaction reduces the required number of terms in the Fourier expansion of the torsional potential for the ground vibrational state from three (in the 2-state fit) to one, only the term in the barrier height is required.     

Vibrational Spectra and Assignments for 3,4-Dibromothiophene

Abstract

The infrared spectrum of 3,4-dibromothiophene has been studied from 4000 to 200 cm^?1. The Laser Raman spectrum has also been recorded and depolarization values have been measured. An assignment of the 21 fundamental vibrations is proposed based on group frequency correlations, Raman polarization data and comparison with the spectra of parent and some halogeno-substituted molecules.     

Rotational and vibrational temperatures measured in a chemiluminescent flame from FTIR Bi2 emission spectra

Rotational and vibrational temperatures of the Bi₂ dimer have been measured in a chemiluminescent flame. Emission spectra of the Bi₂ a³Σ_u⁺(a₁1_u)→X¹Σ_g⁺(X0_g⁺) transition in the near-infrared region were recorded with a FTIR spectrometer. High-resolution spectra of the 0-3, 0-8, 0-9, 2-3, 4-1, 6-0, 6-1, and 7-1 bands served for the determination of the rotational temperature. It was observed that both rotational and vibrational levels are described well by Boltzmann distributions. The average rotational temperature was found to be consistent with the vibrational temperature . The study has shown that such a very heavy molecule as Bi₂ can serve for temperature measurements by optical emission as reported so far only for light molecules.