Broadening and shifting of the 321-, 325- and 380-GHz lines of water vapor by pressure of atmospheric gases

Three spectral lines of the main water molecule isotope in the ground vibrational state located near 321, 325 and 380 GHz were studied at low pressures and room temperature using spectrometer with radio-acoustic detection of absorption. Self-, N₂- and O₂-pressure broadening and shifting parameters of these lines have been precisely measured. A number of parameters, in particular pressure shifts, were obtained for the first time. Complementary study of the 325-GHz line by resonator spectrometer at atmospheric pressure validated the low pressure experiment data and allowed measurement of the 325-GHz line intensity. Obtained results are discussed in comparison with previous experimental and theoretical data.     

Experimental determination of pressure-broadening parameters of millimeter-wave transitions of HNO3 perturbed by N2 and O2, and of their temperature dependences

We report on linewidth measurements on the J=24_K,11−23_K^′,10 and J=38_K,33−37_K^′,32 millimeter wave transitions in the ground vibrational state of nitric acid, located near 470.23 and 544.36 GHz, respectively. Experiments were performed with N₂ and O₂ as perturber molecules, in the 240-350 K temperature range by using a video-type spectrometer. The foreign-gas broadening parameters and their temperature dependence coefficients were determined using the Voigt profile, no narrowing effect being observed. In order to check the reliability of reported values, we carried out measurements on the J=14_K,12−13_K^′,11 transition located near 206.6 GHz, previously observed in two other laboratories. For this last line all the reported values are consistent themselves within one claimed standard deviation.     

Studies of 183 GHz water line: broadening and shifting by air, N2 and O2 and integral intensity measurements

The 3₁₃-2₂₀ rotational transition of water vapor at 183 GHz was studied using modern resonator spectroscopy methods at atmospheric pressures in the broad frequency range 130-205 GHz down to far wings. The experimental method of sample substitution for the exclusion of the apparatus function was used. The air broadening parameter value was defined as 3.84±0.04 MHz/Torr at 298 K. The observed atmosphere water vapor line center was found to be shifted down at about 53 MHz from the line center at low pressures, which gives a value of −0.07±0.02 MHz/Torr for the air pressure shift parameter. Measurements of broadening and shifting of the water line in pure nitrogen and oxygen atmosphere were also performed. Calculated then parameters of air broadening and shifting agree with directly measured ones within the errors quoted. Measurement of the integral intensity of the line was done. The directly measured integral line intensity coincides with a value given in GEISA and HITRAN databases within experimental error. The results are compared with previous experimental laboratory and satellite data.     

Magnetic and microwave absorbing properties of polyaniline/γ-Fe2O3 nanocomposite

The conducting protonated polyaniline (ES)/γ-Fe₂O₃ nanocomposite with the different γ-Fe₂O₃ content were synthesized by in-situ polymerization. Its morphology, microstructure, DC conductivity and magnetic properties of samples were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), four-wire-technique, and vibrating sample magnetometer (VSM), respectively. The microwave absorbing properties of the nanocomposite powders dispersing in wax coating with the coating thickness of 2 mm were investigated using a vector network analyzers in the frequency range of 7–18 GHz. The pure ES has shown the absorption band with a maximum absorption at approximately 16 GHz and a width (defined as frequency difference between points where the absorption is more than 8 dB) of 3.24 GHz, when 10% γ-Fe₂O₃ by weight is incorporated , the width is broadened to 4.13 GHz and some other absorption bands appear in the range of 7–13 GHz. The parameter dielectric loss tan δ_e (=ε″/ε′) in the 7–18 GHz is found to decrease with increasing γ-Fe₂O₃ contents with 10%, 20%, 30%, respectively, but magnetic loss tan δ_m (=μ″/μ′) increases with increasing γ-Fe₂O₃ contents. The results show that moderate content of γ-Fe₂O₃ nanoparticles embedded in protonated polyaniline matrix may create advanced microwave absorption properties due to simultaneous adjusting of dielectric loss and magnetic loss.     

Temperature dependence of pressure broadening of the N = 1− fine structure oxygen line at 118.75 GHz

The absorption profile of the N = 1− fine structure line of oxygen was recorded by a resonator spectrometer at a frequency range of 110-130 GHz at atmospheric pressure and different temperatures ranging from −21 °C up to +22 °C. Analysis of the observed line shape allowed determination of the temperature dependence of the line pressure broadening. The measured value of the temperature exponent is n = 0.74(5) for self-broadening. Consistency of the measurements is supported by simultaneous measurements of the line intensity, the line mixing parameter and the line center frequency, and by comparison of obtained values with previously known data.     

Experimental intensity and lineshape parameters of the oxygen A-band using frequency-stabilized cavity ring-down spectroscopy

Line intensities, self- and air-broadened linewidths, pressure-induced shifts, and collisional narrowing coefficients were measured from 2 ? J′ ? 32 in the P branch of the O₂A-band (12 975-13110 cm⁻¹) utilizing Galatry line profiles. Spectra were recorded using the frequency-stabilized cavity ring-down spectrometer located at NIST, Gaithersburg, MD with a spectral resolution <0.0001 cm⁻¹ and noise-equivalent absorption coefficient of 6 × 10⁻⁸ m⁻¹ Hz^−1/2. Line intensities, obtained from calibrated gas samples for 2 ? J′ ? 32, are ∼1% lower than the values in current spectroscopic databases. At higher J (18 ? J′ ? 32), the measured air- and self- broadened half widths are up to 20% lower than the extrapolated values given in HITRAN 2004, while corresponding half-widths for 2 ? J′ ? 15 are in better agreement. Available self-broadened half widths are fitted to empirical expressions with an rms of 0.8%. We discuss the implications of our results for accurate remote sensing of surface pressure and photon path length distributions.     

Experimental and theoretical investigation on pressure-broadening and pressure-shifting of the 22.2 GHz line of water

Since water is a fundamental component of the atmosphere and it is well established that the accuracy of collisional broadening parameters has a crucial influence on reduction of remote sensing data, we decided to investigate the self-, N₂- and O₂-broadening parameters of the J=6_1,6←5_2,3 (22.2 GHz) rotational transition of water in the temperature range 296-338 K. Due to the relevance of this water line, this investigation should be considered of particular interest in monitoring the Earth's atmosphere, and therefore a particular effort has been made in order to reduce instrumental as well as systematic errors. Experimental determinations have also been supported by theoretical calculations.     

Pressure shift and broadening of 110-101 water vapor lines by atmosphere gases

This paper is devoted to the measurement of pressure shift and broadening parameters of water-vapor lines of the pure rotational transition 1₁₀-1₀₁ in the ground vibrational state of H₂¹⁶O at 556.936 GHz, H₂¹⁷O at 552.02 GHz, H₂¹⁸O at 547.676 GHz, and the vibrationally excited state v₂=1 line of H₂¹⁶O at 658.003 GHz. The broadening coefficients of the line at 556.936 GHz (for N₂ and O₂ as perturbing gases) coincide within the errors with the values obtained recently by Seta et al. [Pressure broadening coefficients of the water vapor lines at 556.936 and 752.033 GHz. JQSRT 2008;109:144-50] by means of a very different technique (THz-TDS). Pressure shift and broadening for other lines were measured for the first time. Comparison of our results with previous measurements and theoretical calculations is presented.     

60-GHz oxygen band: precise broadening and central frequencies of fine-structure lines, absolute absorption profile at atmospheric pressure, and revision of mixing coefficients

The 60-GHz band of ¹⁶O₂ was studied at room temperature and at low (up to 4 Torr) and atmospheric pressures. Precision measurement of central frequencies, self-broadening, and N₂-broadening parameters of fine-structure transitions up to N = 27 was performed by use of a spectrometer with radio-acoustic detection (RAD). The measured parameters are compared with GEISA/HITRAN databanks, MPM92, and other known data. An improved set of the oxygen fine-structure spectroscopic constants is obtained. The absorption profile was recorded in the range 45-96 GHz for laboratory air and pure oxygen at atmospheric pressure by use of a resonator spectrometer with noise level of about ± 0.05 dB/km, and used for deducing the first-order line mixing coefficients and for quantitative assessment of second-order mixing effects. A refined set of MPM parameters is derived from the new data and presented here.     

Microwave spectrum and structure of furfural

The microwave spectrum of furfural was investigated in the frequency range 7 GHz-21 GHz and 49 GHz-330 GHz. The ground and first torsional state of trans-furfural and ground state of cis-furfural were assigned and analyzed. A total of 1720 rotational lines with J up to 100 and K_a up to 53 were assigned to the ground state of trans-furfural, 1406 rotational lines with J up to 100 and K_a up to 48 were assigned to the first torsional state of trans-furfural and 2103 rotational lines with J up to 90 and K_a up to 48 to the ground state of cis-furfural. Accurate sets of centrifugal distortion constants for both conformations have been determined for the first time. The spectra of all ¹³C and ¹⁸O singly substituted isotopic species were observed in natural abundance in the 7 GHz-21 GHz range. Molecular structure co-ordinates, bond lengths and angles of the Kraitchman substitution type (r_s) and pseudo-Kraitchman type (r_pKr) are derived from the isotopic studies.     

Coherence-converted population transfer FTMW-IR double resonance spectroscopy of CH3OD in the OD-stretch region

Rotationally selected infrared spectra of jet-cooled CH₃OD have been recorded and analyzed in the OD-stretch region (2710-2736 cm⁻¹). The observed spectra are obtained by monitoring three E-species microwave transitions (1₋₁ ← 1₀ at 18.957 GHz, 2₋₁ ← 2₀ at 18.991 GHz, and 3₋₁ ← 3₀ at 19.005 GHz) in a narrowband cavity Fourier transform microwave spectrometer, using the background-free coherence-converted population transfer technique. Of the four upper state subbands observed, two (K′ = 0 and −2) are split by perturbations. The E-species deperturbed band origin is at 2718.1 cm⁻¹. The deperturbed reduced term values follow a pattern similar to the ground state. This allows the J′ = 0 torsional tunneling splitting to be estimated as 2.1 cm⁻¹, which can be compared to 2.6 cm⁻¹ in the ground state.     

Organic compounds in the C3H6O3 family: Microwave spectrum of cis-cis dimethyl carbonate

Geometry optimization calculations on 13 members of the C₃H₆O₃ family of organic species have been carried out to determine their relative binding energies. Dimethyl carbonate [(CH₃)₂CO₃] is one of the lower energy species in this family, which includes the C₃-sugars 1,3-dihydroxyacetone and glyceraldehyde. The microwave spectrum of dimethyl carbonate has been measured over the frequency range 8.4-25.3 GHz with several pulsed-beam Fourier-transform microwave spectrometers and from 227 GHz to 350 GHz with direct absorption spectrometers. The spectrum of the lowest-energy cis-cis conformer of dimethyl carbonate has been assigned, and ab initio electronic structure calculations of the three possible conformers have been performed. Stark effect measurements were carried out on the cis-cis conformer to provide accurate determinations of the dipole moment components.     

Complex permittivity,complex permeability and microwave absorption properties of ferrite–polymer composites

The complex permittivity (ε′–jε″), complex permeability (μ′–jμ″) and microwave absorption properties of ferrite–polymer composites prepared with different ferrite ratios of 50%, 60%, 70% and 80% in polyurethane (PU) matrix have been investigated in X-band (8.2–12.4 GHz) frequency range. The M-type hexaferrite composition BaCo⁺²_0.9Fe⁺²_0.05Si⁺⁴_0.95Fe⁺³_10.1O₁₉ was prepared by solid-state reaction technique, whereas commercial PU was used to prepare the composites. At higher GHz frequencies, ferrite's permeabilities are drastically reduced, however, the forced conversion of Fe⁺³ to Fe⁺² ions that involves electron hopping, could have increased the dielectric losses in the chosen composition. We have measured complex permittivity and permeability using a vector network analyzer (HP/Agilent model PNA E8364B) and software module 85071. All the parameters ε′, ε″, μ′ and μ″ are found to increase with increased ferrite contents. Measured values of these parameters were used to determine the reflection loss at various sample thicknesses, based on a model of a single-layered plane wave absorber backed by a perfect conductor. The composite with 80% ferrite content has shown a minimum reflection loss of −24.5 dB (>99% power absorption) at 12 GHz with the −20 dB bandwidth over the extended frequency range of 11–13 GHz for an absorber thickness of 1.6 mm. The prepared composites can fruitfully be utilized for suppression of electromagnetic interference (EMI) and reduction of radar signatures (stealth technology).     

Collision-induced first overtone band of D2 in binary mixtures D2-X where X is Ar, Kr, and Xe

Enhancement spectra of the collision-induced absorption in the first overtone region 5500-6750 cm⁻¹ of D₂ in the D₂-Ar, D₂-Kr, and D₂-Xe binary mixtures were studied at 298 K for base densities of D₂ in the range 55-251 amagat and for partial densities of Ar, Kr, and Xe in the range 46-384 amagat. The observed spectra consist of the following quadrupolar transitions: O₂(3), O₂(2), Q₂ (J), J = 1-5 and S₂ (J), J = 0-5 of D₂. Binary and ternary absorption coefficients were determined from the integrated absorption coefficients of the band. Profile analyses of the spectra were carried out using the Birnbaum-Cohen (BC) lineshape function and characteristic lineshape parameters were determined from the analyses.     

N2-, H2-, and He-induced collisional broadening of the J = 24 ← 23 transition of HC3N located near 218.3 GHz at different temperatures

We report on experimental collisional relaxation of the J = 24 ← 23 line of HC₃¹⁴N, located near 218.3 GHz, induced by nitrogen, hydrogen, and helium. The measurements were carried out at selected temperatures in the 235-350 K range using a video-type spectrometer. The foreign gas broadening parameters and their temperature dependences were determined assuming Voigt lineshape profiles and the usual T⁻ⁿ temperature law. The experimental broadening parameters are compared with results derived using the ATC collisional formalism.     

FTMW spectroscopy of jet-cooled 9-cyanoanthracene

Rotational spectrum of jet-cooled 9-cyanoanthracene has been observed in the 4-8 GHz region with a Fourier-transform microwave spectrometer. The present observation of 25 low-J transitions with J^′′?11 has confirmed the previous results on the rotational constants of the ground state determined by rotational coherence spectroscopy [J. Phys. Chem. A. 105 (2001) 1131] and provided the values with significantly improved precision. An accurate set of hyperfine splitting constants is also reported for the ¹⁴N nuclear quadrupole coupling. The electric dipole moment was determined from Stark effect measurements on several split components: μ_b(=μ)=4.406(7) D.     

Millimeter-wave spectrum of 2,3-difluorobenzonitrile and ab initio DFT calculations

The ground vibrational state rotational spectrum of 2,3-difluorobenzonitrile has been reinvestigated in the frequency range 40.0-99.0 GHz. High J and K₋₁ (J ? 62 and K₋₁ ? 20) transitions have been measured and analyzed to determine accurate rotational and centrifugal distortion constants. Finally, the experimental values were compared with the corresponding values computed at the DFT-B3PW91/6-31g(d,p) level of theory. A very good agreement has been found.     

Magnetic and electromagnetic properties of composites of iron oxide and Co-B alloy prepared by chemical reduction

Magnetic and electromagnetic properties were investigated on the composites of iron oxide and Co-B alloy, which were prepared by a modified chemical reduction method. The composites are characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDXA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and vibrating sample magnetometry (VSM). The complex electromagnetic parameters (permittivity ε_r=ε_r′+jε_r″ and permeability μ_r=μ_r′+jμ_r″) of paraffin mixed composite samples (paraffin:composites=1:1 in mass ratio) were measured in the frequency range 2-18 GHz by vector network analyzer. The measured real part (ε_r′) and imaginary part (ε_r″) of the relative permittivity show two resonant peaks in the range of 2-18 GHz. The imaginary parts of relative permeability (μ_r″) of all samples exhibited one broad resonant peak over the 2-8 GHz range. The μ_r″ of samples with higher molar ratio of Co to Fe (C and D) shows negative values within 13-18 GHz, which exhibit resonant and antiresonant permeabilities simultaneously. Calculation results indicated that the reflection loss values of the composites and paraffin wax mixtures are less than −10 dB with frequency width of about 6 GHz at the matching thickness.     

Preparation and microwave-absorbing properties of NiFe2O4-polystyrene composites

NiFe₂O₄ nanoparticles were synthesized by the polyacrylamide gel method with acrylamide as the monomer and N,N′-methylenediacrylamide as lattice agent. The average crystallite sizes of the nickel ferrites annealed at 500, 600 and 800 °C are about 10, 30 and 50 nm, respectively. Ferrite-polystyrene composites were made by hot pressing, and microwave-absorbing properties of the composites with different contents of 35, 45, 55 and 65 wt% ferrite were investigated by testing complex permeability and complex permittivity in the X-band (8.2-12.4 GHz) frequency range. All the parameters, ε′, ε″, μ′ and μ″, increase with increasing ferrite content. The reflection losses were calculated based on a model of a single-layered plane wave absorber backed by a perfect conductor. The composite with 65 wt% ferrite content shows a minimum reflection loss of −13 dB at 11.5 GHz with a −10 dB bandwidth over the extended frequency range of 10.3-13 GHz for an absorber thickness of 2 mm.     

Experimental study of the line mixing coefficient for 118.75 GHz oxygen line

The oxygen fine structure line 1− at 118.75 GHz was studied by two spectrometers at low (0.2-3.5 Torr) and high (atmosphere) pressures in air and pure oxygen. Improvement in the spectrometer with BWO and acoustic detector included use of a powerful (more than 40 mW) radiation source. Improvement in the modern resonator spectrometer included exclusion of apparatus function by sample substitution and a wider (110-130 GHz) scanned frequency range. As a result, the 1− oxygen line was observed by both spectrometers with high (up to 450) signal-to-noise ratio which permitted precise measurements of the line parameters. The investigation separated linear- and quadratic-with-pressure displacement of the line center. The line mixing coefficient responsible for apparent quadratic dependence of the center frequency on pressure was measured experimentally for the first time for this line. The line mixing coefficient was measured at 297 K as −4.62(38)×10⁻⁵ Torr⁻¹ for pure oxygen and −5.9(29)×10⁻⁵ Torr⁻¹ for air, compared to the previously calculated value −3.1×10⁻⁵ Torr⁻¹. Linear dependence of the line center frequency on pressure does not exceed ±20 kHz/Torr for air and ±10 kHz/Torr for pure oxygen. Refined values of line broadening were obtained. Integral intensity of the line was measured. A comparison with the previous investigations is presented. Inconsistencies in published data about pressure line shifts of oxygen molecule spectral lines are discussed.