Microwave absorption coefficients of atmospheric pollutants and constituents

Calculations of the transition frequencies and absorption coefficients of microwave rotational transitions are given for a number of atmospheric pollutants and constituents. New measurements of the absorption coefficients are made in the vicinity of 70 GHz. The apparatus used in these measurements is briefly described. The calculated absorption coefficients are compared with these measurements and with existing measurements at other frequencies where available. Transitions with frequencies up to about 200 GHz are considered for the molecules and radicals SO₂, O₃, H₂O, NO₂, H₂S, H₂CO, NH₃, CO, OCS, N₂O, NO, OH, O₂, SO. Also discussed are criteria for the selection of appropriate transitions for the development of high sensitivity monitors to be used in air pollution and combustion research.     

Absorption coefficients of sulfur dioxide microwave rotational lines

New calculations of the absorption coefficients of the rotational transitions of ³²S¹⁶O₂ are given for all energy levels up to J = 50 and frequencies less than 200 GHz. A spectrometer incorporating a semiconfocal Fabry-Perot resonant cavity and operating in the vicinity of 70 GHz is described. The calculated absorption coefficients are compared to measured values obtained with this spectrometer and to existing measurements over the frequency range 26–40 GHz. The results obtained are in general agreement to within 5–10%. A detailed knowledge of the absorption coefficient behavior as a function of frequency is of particular interest in the development of high-sensitivity SO₂ monitors, and in investigations of the kinetics of fast chemical reactions.     

Millimeter and submillimeter wave absorption by atmospheric pollutants and constituents

Calculated absorption coefficients and rotational transition frequencies ara given for a number of polar molecules of interest to pollution and energy research. The results, which are presented in graphical form for microwave frequencies up to 1400 GHz, illustrate the increased absorption line intensities occurring in the submillimeter region. For most species, these absorption coefficients attain their maximum values in this region. Included in the calculations are SO₂, H₂CO, O₃, H₂O, H₂S, OCS, CO, NO, OH, SO, NH₃, and CS. A discussion of the techniques currently available for detection in the submillimeter region of these species is also given.     

Spin dynamics and structural phase transitions in quasi-2D antiferromagnets R2CuO4 (R=Pr, Sm, and Eu)

Spin and lattice dynamics of R₂CuO₄ (R=Pr, Sm, and Eu) crystals were studied over the frequency and temperature ranges 20–250 GHz and 5–350 K, respectively. The absorption coefficients of the R₂CuO₄ crystals (R=Pr, Sm, and Eu) were found to change dramatically at temperatures of, respectively, 20, 80, and 150 K over a broad frequency range above 120 GHz. The absorption jumps were caused by the structural phase transitions. Broad spin-wave bands were observed in the high-temperature phases of all crystals studied. Absorption lines due to lattice dynamics were observed near the temperatures of structural phase transition over a broad frequency range, including the frequencies corresponding to the spin-wave bands.     

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.     

Anomalous absorption in H<Subscript>2</Subscript>CN and CH<Subscript>2</Subscript>CN molecules

Structures of H₂CN and CH₂CN molecules are similar to that of H₂CO molecule. The H₂CO has shown anomalous absorption for its transition 1₁₁–1₁₀ at 4.8 GHz in a number of cool molecular clouds. Though the molecules H₂CN and CH₂CN have been identified in TMC-1 and Sgr B2 through some transitions in ortho as well as in para species, here we have investigated the condition under which transitions 1₁₁–1₁₀ and 2₁₂–2₁₁ of these molecules may show anomalous absorption. For the present investigation, we have calculated energy levels and radiative transition probabilities. However, we have used scaled values for collisional rate coefficients. We found that relative values of collisional rate coefficients can produce the required anom-alous absorption in 1₁₁–1₁₀ and 2₁₂–2₁₁ transitions in the molecules.      

Assignments of fir laser emissions from CH3OH optically pumped by an intra-cavity etalon tuned TEA-CO2 laser

The author reports that TEA-CO₂ with an intra-cavity etalon is a useful pumping source which can deliver widely tunable beam (tunable range 1 GHz) with accurate oscillation frequencies and with high power compared to a tunable wave guide laser.The source is applied to the excitations of CH₃OH and the FIR emissions from it are well assigned for there absorption transitions and FIR emissions. This proves that the source display not only usefulness for development of new FIR emissions but also for molecular spectroscopy.     

Linear dynamics of a magnetic subsystem in a quasi-Ising magnet

Microwave absorption at frequencies from 37 to 85 GHz was studied for a Dy_0.3Y_2.7Fe₅O₁₂ single crystal in pulsed magnetic fields of up to 30 T at T=4.2 K. The magnetic field was aligned with the [100] direction. For the fields above 4 T, several soft magnetic-resonance modes were observed, most of them being caused by the static phase transitions induced by a strong external magnetic field. The field-independent absorption lines away from the points of phase transition may be due to the dynamic Jahn-Teller magnetic effect.     

Infrared-microwave two-photon spectra of the ν3 bands of 12CH3F and 13CH3F

Infrared-microwave two-photon spectra have been obtained for the ν₃ bands of ¹²CH₃F and ¹³CH₃F with a two-photon spectrometer employing a CO₂ laser and a computer-coupled microwave source operating in the 8–18 GHz region. Even though the intensities of the spectra for the double parity levels in these molecules are inversely proportional to the square of the microwave frequency, transitions have been observed with microwave frequencies of up to 16 GHz. Comparison of these observed two-photon frequencies to frequencies predicted from infrared laser Stark spectroscopy, and to frequencies calculated from vibration-rotation parameters obtained by fitting these and other frequencies, shows agreement to within a few MHz. Spectroscopic parameters for the ground and ν₃ excited states of the two species are reported.     

THz Spectrum of Methanol-D4 and Microwave Spectrum of Methanol-D1

The sub-THz spectra of CD₃OD have been observed in the frequency ranges of 461-486 GHz and 596-610 GHz using the Backward Wave Oscillator based Technique. The 218 transitions of CD₃OD are newly assigned to J=31 and K=12 in the first three torsional states (n=2). The assigned lines include several new series of both a-type and b-type transitions. These THz transitions combined with the previous published millimeter-wave (MMW) and microwave (MW) data and recently observed high resolution Fourier transform far infrared (FIR) spectra have been used in a global fit. The data set contains 1320 MW, MMW, SMMW and FIR transitions with n=2, J=31 and K=12. Using the reduced torsion-rotational Hamiltonian with 67 parameters the fit converges with an RMS deviation of 277 kHz for the MW transitions and of 0.00024 cm^-1 for the FIR transitions. Thus molecular parameters are well determined. The MW spectrum of CH₂DOH (in the range 97.7 -118.0 and 128.5-146.5 GHz) is also presented which will help astronomers for astrophysical detection and theoretical spectroscopists to get further information on torsion-rotation-vibration interaction in an internal rotor with an asymmetric top.     

Intracavity absorption of CO2 laser radiation by chlorofluorocarbon (CFC) gases

Intracavity absorption method was applied to determine the absorption coefficients of trichlorofluorocarbon CCl₃F (CFC-11), dichlorodifluorocarbon CF₂Cl₂ (CFC-12) and chlorodifluorocarbon CHClF₂ (CFC-22) vs. the pressure in the cell inside the cavity of a tunable CO₂ laser at different spectral lines on branches 9R and 10P.The laser output power was measured vs. the gas pressure at different spectral lines on branches 9R, 9P, 10R and 10P of CO₂ molecule transitions. A strong absorption was observed for lines of 9R and 10P branches, whereas a weak absorption was noticed for lines of 9P and 10R branches.The calculation of absorption coefficients was restricted for 9R and 10P due to the oscillating variation of the output power of CO₂ laser vs. the CFC pressure, which was occurred for the lines of 9P and 10R.On the basis of absorption coefficients, the absorption cross-sections for CFC-12 were calculated and compared with the absorption cross-sections found from the previous experiment (where the cell was located outside the cavity), NIST and HITRAN databases, respectively.The obtained data could be useful for CFC gases detection as pollutants in the atmosphere.     

Stark spectroscopy of 13CD3OH with the HCN laser

The laser Stark spectrum of ¹³CD₃OH has been studied using the 311 μm line of the HCN laser. An extensive series of absorption lines has been observed and assigned to the J = 3 to 11 members of the K = 2 ← 3E₁, Q-branch transition in the v_t = 1 excited torsional state. Zero-field frequencies for all the assigned transitions are given with improved accuracy over those calculated from available molecular constants. For the Q-branch series, the branch origin and the series expansion coefficients are also presented.     

Laser Stark saturation spectroscopy in methyl alcohol

The method of Lamb dip spectroscopy in Stark tuned molecular gases is discussed and applied to the experimental assignment of methyl alcohol infrared transitions in the ₅ C–O stretch band. Theoretical expressions for Stark Lamb dip patterns are derived for P, Q and R-branch transitions. Stark tuning results and transition quantum number assignments are presented for several 10m transitions, along with measured values of resonant frequencies, absorption coefficients and pressure broadening coefficients.Work supported by the Army Research Office, Durham, and the National Science Foundation.     

Multi-species laser absorption sensors for in situ monitoring of syngas composition

Tunable diode laser absorption spectroscopy sensors for detection of CO, CO₂, CH₄ and H₂O at elevated pressures in mixtures of synthesis gas (syngas: products of coal and/or biomass gasification) were developed and tested. Wavelength modulation spectroscopy (WMS) with 1f-normalized 2f detection was employed. Fiber-coupled DFB diode lasers operating at 2325, 2017, 2290 and 1352 nm were used for simultaneously measuring CO, CO₂, CH₄ and H₂O, respectively. Criteria for the selection of transitions were developed, and transitions were selected to optimize the signal and minimize interference from other species. For quantitative WMS measurements, the collision-broadening coefficients of the selected transitions were determined for collisions with possible syngas components, namely CO, CO₂, CH₄, H₂O, N₂ and H₂. Sample measurements were performed for each species in gas cells at a temperature of 25 °C up to pressures of 20 atm. To validate the sensor performance, the composition of synthetic syngas was determined by the absorption sensor and compared with the known values. A method of estimating the lower heating value and Wobbe index of the syngas mixture from these measurements was also demonstrated.     

Microwave permittivity and phase transitions in Cs2HgBr4 and [(CH3)4N]2CuCl4

Phase transitions in the compounds Cs₂HgBr₄ and [(CH₃)₄N]₂CuCl₄ have been observed by the study of complex permittivity at frequencies of 37 GHz. These observations are compared with previous results on these compounds obtained with other techniques such as DTA.     

Diode laser measurements of temperature-dependent collisional-narrowing and broadening parameters of Ar-perturbed H2O transitions at 1391.7 and 1397.8 nm

High-resolution absorption lineshapes of two H₂O transitions near 7185.60 and 7154.35 cm⁻¹ have been recorded in a heated static cell as a function of temperature (296-1100 K) and pressure (6-830 Torr) using two distributed-feedback diode lasers. The measured absorption spectra are least squares fit to both Voigt and Galatry profiles. Strong collisional-narrowing effects are observed in the Ar-broadened H₂O spectra at near-atmospheric pressure due to the relatively weak collisional broadening induced by Ar-H₂O collisions, while collisional narrowing is not significant for pure H₂O absorption lineshapes. Line strengths and self-broadening coefficients are inferred from the pure H₂O absorption spectra and compared with published data. Temperature dependences of the Ar-induced broadening, narrowing, and shift coefficients are determined using Galatry fits to the absorption data. The measured collisional-narrowing parameters have similar temperature dependence to the collisional-broadening coefficients.     

Multi-species detection using multi-mode absorption spectroscopy (MUMAS)

The detection of multiple species using a single laser and single detector employing multi-mode absorption spectroscopy (MUMAS) is reported. An in-house constructed, diode-pumped, Er:Yb:glass micro-laser operating at 1,565 nm with 10 modes separated by 18 GHz was used to record MUMAS signals in a gas mixture containing C₂H₂, N₂O and CO. The components of the mixture were detected simultaneously by identifying multiple transitions in each of the species. By using temperature- and pressure-dependent modelled spectral fits to the data, partial pressures of each species in the mixture were determined with an uncertainty of ±2 %.     

A Fixed-Tuned W-Band Waveguide SIS Mixer with 4.0-7.5 GHz IF

The design and performance of a fixed-tuned W-band SIS mixer with a wide band IF of 4.0-7.5 GHz is presented. Waveguide-to-stripline transition of the SIS mixer is designed using the lumped-gap-source port provided by HFSS^TM. Measured receiver noise temperature is less than 25 K in the frequency range of 95-120 GHz, with a minimum value of around 19 K achieved. Mixer noise temperature is determined to be about 8.5 K, which is around twice the quantum limit (i.e., 2hw/k). In spite of the high IF frequencies (f ₀ = 6 GHz), the performance of the SIS receiver is comparable or even superior to those of the best mechanically-tunable waveguide SIS receivers at low IF frequencies (f ₀ = 1.5 GHz). This result suggests that it is easy to design waveguide-to-stripline transitions without scale-model measurements.     

Analysis of the Line Profiles of CH3CN for theJ= 5 ← 4 andJ= 6 ← 5 Rotational Transitions

The pressure broadening, pressure shift coefficients, and absolute intensities have been obtained for theJ= 6 ← 5 and theJ= 5 ← 4 absorption lines of acetonitrile CH₃CN at 110 and 92 GHz, respectively. The absorption line shapes have been directly recorded modulating the radiation beam by an optical chopper. In addition to the self-effects, the foreign-broadening coefficients have also been measured for N₂, O₂, and Ar.     

Absorption profiles of HCl for the J = 1-0 rotational transition: Foreign-gas effects measured for N2, O2, and Ar

Line profiles of the J = 1-0 transition of the hydrogen chloride, H³⁵Cl and H³⁷Cl isotopomers, were measured with a BWO-based submillimeter-wave spectrometer at AIST in real form: three hyperfine transitions for each isotopomer, i.e., total six lines at 625 and 626 GHz. The effect of foreign gases on the broadening and shift was determined for N₂, O₂, and Ar. The modified Voigt function was applied as the line shape function for preliminary analysis, where the collisional-narrowing effect was clearly observed. In the final analysis, we applied the Galatry function and determined the integral intensity, line center position, Lorentzian width, and contraction parameter for each absorption line. The magnitudes of the foreign-gas pressure-broadening coefficients decrease in order of N₂, O₂, and Ar. The line-shift coefficients were clearly observed, the magnitudes of which decrease in order of Ar, O₂, and N₂. The pressure dependence of contraction parameter was determined, although with poor precision.