Submillimetre EPR spectrometer

A wide-band submillimetre EPR spectrometer is described. A set of tunable backward wave oscillators and quasioptic lens system enables one to operate in the frequency region 79–535 GHz. The sample is placed in a magnetic field of up to 1 T at 4.2 K. The spectrometer is intended for the investigation of EPR spectra of rare-earth ions in solids with zero field splittings of the ground states near the frequency of operation and/or electron systems with ag-factor exceeding 5. The spectrometer’s capabilities are demonstrated with an investigation of the EPR spectra of Dy²⁺ and Dy³⁺ ions in CaF₂. As a result the exact value of the zero field splitting between the ground Γ₈ quartet and the first exited Γ₇ doublet of Dy³⁺ in CaF₂, Δ=257±0.5 GHz, has been measured directly.     

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.     

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.     

Collisional broadening and shifting of OCS rotational spectrum lines

Broadening and shifting of carbonyl sulfide (OCS) rotational spectrum lines by pressure of N₂, O₂ and OCS were accurately studied in the frequency range 24–850 GHz at room temperature using a spectrometer with radio-acoustic detection of absorption. Rotational dependences of collisional widths of OCS spectrum lines were determined by a simple empirical polynomial fit of experimental data. Experimental uncertainties were analyzed. Results of supplementary test measurements of self-broadening of rotational OCS lines in the ν₂ excited vibrational state and carbon monoxide (CO) lines in the ground vibrational state are presented. Comparison of the obtained results with previously known measurements and theoretical calculations is given. The performed work allows for the first time development of accurate gaseous etalon of absorption for atmospheric applications and laboratory use, covering continuously the whole millimeter- and submillimeter-wave range.     

A superior microwave absorption material: Ni2+-Zr4+ Co-Doped barium ferrite ceramics with large reflection loss and broad bandwidth

Large reflection loss and wide bandwidth are significant targets, determining the microwave absorption ability. However, it is still a challenge to simultaneously satisfy the two conditions. As a multifunctional material, BaFe₁₂O₁₉ possess excellent electromagnetic properties in the microwave frequency band. Due to the natural resonance phenomenon of the material, BaFe₁₂O₁₉ can produce a large magnetic loss which correlates with Fe³⁺ content, and the microwave absorption characteristics of barium ferrite can be modulated by ion doping. As a typical magnetic metal, Ni coupled with high-valence state Zr⁴⁺ doping helps to produce double resonance peaks. In this work, Ni²⁺-Zr⁴⁺ co-doping M-type barium ferrites (BaFe_12-2xNi_xZr_xO₁₉, BNZFO-x, x = 0–0.8) were prepared conveniently by solid-state reaction method. Several necessary measurements to characterize its microwave absorption property have been operated such as morphology, magnetic performance and electromagnetic parameters. The results show that reflection loss and bandwidth can be simply tuned by tailoring Ni²⁺-Zr⁴⁺ content. The reflection loss peak drifts from 18 GHz to 9.76 GHz, which involves a half of the studied frequency range. The maximum reflection loss achieves −60.6 dB and the corresponding bandwidth over −10 dB is 7.68 GHz for BNZFO-0.6 ceramic with only 2.1 mm thickness. Thus, the doping of Ni²⁺-Zr⁴⁺ ion pairs is beneficial to improve the absorbing properties of the material, and the superior microwave absorption property may originate from its inner double natural resonance in micro-scale. The excellent microwave absorption properties suggest that BNZFO-x is a promising candidate applied for designing electromagnetic shielding devices.     

Development of the physical principles of the design and implementation of a 500–700 GHz spectrometer with a superconducting integrated receiver

A spectrometer based on the effect of freely decaying polarization in the frequency range 500–700 GHz has been designed. Radiation sources are harmonics from a quantum semiconductor superlattice frequency multiplier. The receiving system of this spectrometer is constructed using a superconducting integrated receiver based on a superconductor-insulator-superconductor mixer and a flux-flow oscillator operating as a heterodyne oscillator. The spectrometer has been used to measure absorption lines of NH₃ in a sample of expired air (572 GHz).     

Electronic structure and magnetic and electromagnetic wave absorption properties of BaFe12-xCoxO19 M-type hexaferrites

Crystal, electronic structures and the magnetic and electromagnetic wave absorption properties of BaFe_12-xCo_xO₁₉ (x = 0–2) M-type hexaferrites prepared by a co-precipitation technique were studied. The analyses of X-ray diffraction patterns indicated that the samples mainly crystallized in the P6₃/mmc hexagonal structure, with the additional constitution of Y-type hexaferrite as x > 0. The replacement of Co²⁺ for Fe³⁺ in BaFe_12-xCo_xO₁₉ changed the lattice constants and caused lattice distortions. Particularly, Co²⁺ doping also reduced magnetization and hard magnetic property of BaFe_12-xCo_xO₁₉. This is ascribed to magnetic moment of Co²⁺ smaller than that of Fe³⁺ and to the decrease of magnetocrystalline anisotropy. Having studied electromagnetic wave absorption properties in the frequency range f = 0.1–18 GHz, we found BaFe_12-xCo_xO₁₉ showing high reflection loss (RL) values at frequencies of 0.1–15 GHz, but fairly low RL values at higher frequencies. These features suggest that BaFe_12-xCo_xO₁₉ can be suitable to electronic devices working at GHz frequencies.     

Investigation of the temperature dependence for the spectra of supercooled water in the middle infrared

The temperature dependence of the bending ν₂, combination ν₂ + ν _L , and stretching (ν₁, ν₃, 2ν₂) absorption bands in the infrared spectra of supercooled water with a temperature-change step Δt from 2 to 2.5°C was studied using an advanced infrared Fourier spectrometer. It was found that the frequency of the maximum of the stretching absorption band (2700–3700 cm^?1) decreases with the reduction of the water temperature from ?0.5 to ?5.0°C. The frequency of the maximum of the combination absorption band (2130 cm^?1) increases with the reduction of the water temperature in a range from ?3.0 to ?5.0°C. The frequency of the maximum of the absorption band of bending oscillation (1640 cm^?1) is invariable with a reduction of the water temperature from ?0.5 to ?5.0°C.     

The vibration-rotation HDO absorption spectrum between 8558 and 8774 cm−1

The absorption spectrum of HDO has been recorded in the region 8558–8774 cm^?1 using a high-sensitivity intracavity F₂^?:LiF center laser spectrometer. The absorption sensitivity is 10^?7 cm^?1 and the line-center determination accuracy is about 4 × 10^?2 cm^?1. The spectrum was interpreted and the absorption lines were attributed to the ν₂ + 2ν₃ band of HDO. Energy levels up to J = 12 and rotational and centrifugal parameters of the vibrational (012) state were obtained.     

Wide band (2.5 GHz) infrared heterodyne spectrometer

Conclusion A double beam heterodyne spectrometer with 2.5 GHz bandwidth was built in Reims. The receiver's bandwidth was measured by heterodyning radiation from a CO₂ laser with the radiation from a tunable diode laser. The spectrometer was used for laboratory studies. Ammonia absorption spectra were recorded. Line positions in agreement with other works were measured.This apparatus will soon be used for atmospheric ozone studies in association with an isotopic¹²C¹⁸O₂ laser to avoid atmospheric CO₂ absorption.     

Diode-laser spectroscopy of supersonic free jets

A supersonic-free-jet infrared spectrometer has been constructed for investigation of molecular vibrational spectra at low rotational and vibrational temperatures. The sensitivity of measurement in a pulsed jet is increased by employing a phase-sensitive detection method synchronized with the pulse frequency. The performance of the spectrometer is examined for the absorption lines of the NH₃ v ₂ band. A rotational temperature as low as 16K is attained when seeded in He. Cold-jet spectra are demonstrated for thev ₃ bands of PF₅,³⁴SF₆, and¹⁸²WF₆.     

Laser stark spectroscopy of the ν2 fundamental band of 15NH3

The ν₂ fundamental band of ¹⁵NH₃ has been observed with a laser Stark spectrometer in Doppler-limited resolution. A set of 38 band constants including the electric dipole moment and its rotational dependence are determined from 416 Stark resonances observed in the present work and three submillimeter lines reported in the literature. The ν₂-band absorption line frequencies in the region 800–1160 cm⁻¹ and their relative absorption intensities are estimated from the band constants.     

Study of the phase transition in the ionic conductor CuTeBr by millimeter wave spectroscopy

By use of a quasi-optical, broad-banded spectrometer in the frequency range of 40–90 GHz (λ = 7.5 ? 3.3 mm), the temperature dependence of absorption of the ionic conductor CuTeBr has been investigated for the first time. An abrupt and reversible jump in absorption independent of the incident frequency is observed at (69 ± 2)°C. This is attributed to a first order phase transition from an orthorhombic superstructure to a tetragonal structure. The results are discussed in connection with the high ionic conductivity of this material.     

Wide-band EPR spectroscopy of YAlO3: Tm3+ single crystals

The YAlO₃: Tm³⁺ single crystal has been studied on a wide-band EPR spectrometer. The EPR spectra of Tm³⁺ ions in the frequency range of 90–160 GHz have been detected for the first time. It has been confirmed that thulium ions substitute the position of Y³⁺ in the crystal lattice. The detected spectra have been described with the use of a spin Hamiltonian with the effective spin S = 1/2. A comparative analysis of the orientation of the magnetic axes of the Tm³⁺ paramagnetic center with earlier data on other rare-earth ions has been performed.     

Rydberg states in the D layer of the atmosphere and the GPS positioning errors

The noncoherent radiation in the frequency range 0.8–8.0 (GHz) formed in the D layer of the ionosphere at high solar activity due to transitions between Rydberg states is considered. The emitting layer thickness located 80–110 km above ground surface is estimated. A complicated irregular behavior of the frequency dependence of the radiation intensity for different values of å electron concentration n _e and temperature T _e due to different characteristics of electron scattering on the nitrogen and oxygen molecules is revealed. The dependences of the flux power of UHF radiation from the D layer in the indicated frequency range on the concentration and temperature of free electrons are calculated. It is shown that, at a frequency of ν = 1.44 GHz, the UHF radiation spectrum features a characteristic waist point, the position of which is almost independent of the electron temperature T _e ; i.e., a one-parameter dependence of the power flux on the electron n _e density takes place. In the frequency range of 4.0–8.0 GHz, the radiation spectrum exhibits a family of curves that, for each value of n _e and a wide range of T _e , give rise to a relationship known as the “bottleneck.” It was found that, with increasing frequency, the bottleneck moves upwards along a curve described by a quadratic dependence on the radiation frequency. For a frequency of ～5 GHz, and a certain range of temperature T _e and electron concentration within 5 · 10³ cm^?3 < n _e < 2 · 10⁴ cm^?3, an almost linear dependence of the UHF radiation power on n _e is observed. A comparative analysis of GPS signal delays at frequencies ν _f ⁽¹⁾ = 1.57 and ν _f ⁽²⁾ ≈ 5 GHz for various states of the ionosphere is performed. It is shown that, under the same condition, the use of the second frequency is more advantageous and informative. The ways of further development of the theory and experiment in studying the role of quantum resonant properties in the distortion of global satellite positioning system signals and in solving the fundamental problem of their elimination are discussed.     

A study of the fundamental and first overtone bands of NO in NO-rare gas mixtures at pressures up to 10,000 PSI

The absorption intensities of the 1-0 and 2-0 vibration-rotation bands of NO are determined from the absorption coefficients of NOHe and NOAr gaseous mixtures at high pressures at room temperature. The values obtained are: A_1-0 = 121 ± 6 cm^?2 Agt^?1 and A_2-0 = 2.17 ± 0.11 cm^?2 Agt^?1. A theory developed by Tipping is applied to evaluate the dipole moment coefficients unambiguously, including their signs, from the absolute intensity values and the difference between the mean frequency factor and the band origin. The following expansion for the dipole moment function in the ground state of NO is determined: M(x) = ?0.166 + 2.54x ? 1.99x² (in Debye). The absorption profiles of both the 1-0 and 2-0 bands in NOAr mixtures show marked changes as gas pressure increases; some of the factors influencing the shapes of the bands are also discussed. The plots of the integrated intensity vs rare gas density are found to be straight lines with positive slopes. This linear increase of the band intensity with density is interpreted as mainly due to the apparent induced absorption.     

Absolute diode-laser frequency calibration using varactor mixing with a stabilized CO2 laser. Ozone spectrum near the 9R6 CO2 frequency

Efficient infrared varactor mixing near 9 μm has been performed between diode-laser and CO₂ laser. Difference frequency up to 17 GHz has been detected using non linear mixing between the two radiations and the first four harmonics of a microwave frequency (f = 4.2 GHz). As a result, the absorption spectrum of ozone near the 9R₆ CO₂ line is frequency scaled over a 1.7 cm^-1 range with microwave accuracy.     

Millimeter-wave spectrum of BrCN produced by dc discharge

Ground state (v=0) and first excited state (v=1) millimeter-wave rotational absorption spectra of cyanogen bromide (BrCN) and some of its isotopic species, have been investigated in the frequency region: 40.0-75.0 GHz using a source-modulated millimeter-wave spectrometer. Millimeter-wave radiation has been produced using a frequency multiplier, the fundamental radiation source being klystrons. BrCN has been produced by applying a dc glow discharge through a mixture of 3-bromobenzonitrile and trifluoromethylbromide (CF₃Br) at low pressure. The quadrupole hyperfine structure of ⁸¹Br and ⁷⁹Br have been resolved, measured, and analyzed. Finally, internuclear distances of BrCN have been determined.     

New Measuring Apparatus for Complex Permittivity at Millimeter-Wave Frequencies

A dielectric rod resonator excited by a nonradiative dielectric waveguide is used for measuring complex permittivity of low loss dielectric materials. The complex permittivties of single crystal sapphire, polycrystalline Ba (Mg_1/2 W_1/2) O₃ and Mg₂ Al₄ Si₅ O₁₈ (cordierite) have been obtained at 60 and 77 GHz by the new apparatus. The first time the measurement results of complex permittivity of brain grey and white matters from 15 to 50GHz utilizing a two-port microstrip test fixture is presented. S-parameters of Test fixture are simulated employing the finite-element method. A new spectrometer for the precision measurement of dielectric permittivity and loss tangent, which is capable of providing high resolution data for the first time over an extended W-band (68-118 GHz) frequency for specimens with a large range of absorption values, including highly absorbing specimens that otherwise would not be possible.     

Saturated absorption Stark spectroscopy of CH3OH with CO2 lasers

The vibration-torsion-rotation spectrum of CH₃OH has been studied by saturated absorption spectroscopy in applied electric fields up to 20 kV/cm, using ¹²C¹⁶O₂ and ¹²C¹⁶O₂ lasers. Frequency offsets for 129 absorption lines were measured relative to the frequency of a fluorescence stabilized reference laser with an accuracy of ±0.5 MHz for 75 lines inside the ±40 MHz tuning range and 2–5% for lines located up to 1.2 GHz outside the tuning range, but Stark tuned into resonance. For 36 lines we obtained fully-resolved Stark spectra, allowing determination of both lower and upper state K. Using this information in combination with information available from optically-pumped FIR laser emission, a total of 44 lines were completely assigned as transitions involving torsional n = 0, 1, 2 and 3 states of the CO stretch. Certain states belonging to n = 1 displayed an anomalous Stark effect which is at present not understood.