Terahertz absorption spectra of nitromethane

Nitromethane, with its heavy frame and internal rotator, readily evaporates into the atmosphere making it an ideal candidate for remote sensing. Here we present the absorption spectra of gas-phase nitromethane between 9 and 50 cm⁻¹. Measurements were taken using a Bruker IFS 66v Fourier transform far-infrared (FTIR) spectrometer at a resolution of 0.12 cm⁻¹ (0.0036 THz) from 9 to 40 cm⁻¹ and a Bruker Vertex 80v FTIR spectrometer with a resolution of 0.0075 cm⁻¹ (0.00226 THz) from 10 to 50 cm⁻¹. The absorption spectra were measured at multiple pathlengths ranging from 2 to 6 m. These measurements were used to calculate the absorption coefficient of nitromethane as a function of wavenumber.     

New measurements of the water vapor continuum in the region from 0.3 to 2.7 THz

We present a spectroscopic study of the water vapor continuum absorption in the far-IR region from 10 to 90 cm⁻¹ (0.3-2.7 THz). The experimental technique combines a temperature-stabilized multipass absorption cell, a polarizing (Martin-Puplett) interferometric spectrometer, and a liquid-He-cooled bolometer detector. The contributions to the absorbance resulting from the structureless H₂O-H₂O and H₂O-N₂ continua have been measured in the temperature range from 293 to 333 K with spectral resolution of 0.04-0.12 cm⁻¹. The resonant water vapor spectrum was modeled using the HITRAN04 database and a Van Vleck-Weisskopf lineshape function with a 100 cm⁻¹ far-wing cut-off. Within experimental uncertainty, both the H₂O-H₂O and H₂O-N₂ continua demonstrate nearly quadratic dependencies of absorbance on frequency with, however, some deviation near the 2.5 THz window. The absorption coefficients of 3.83 and 0.185 (dB/km)/(kPa THz)² were measured for self- and foreign-gas continuum, respectively. The corresponding temperature exponents were found to be 8.8 and 5.7. The theoretically predicted foreign continuum is presented and a reasonable agreement with experiment is obtained.     

Generation of high average power 1 kHz shaped THz pulses via optical rectification

Generation of near single-cycle THz pulses from lithium niobate with 3.3 μJ energy, 3.3 mW average power, 1.2 THz central frequency and 4 MW peak power was demonstrated by tilting the intensity front of the pump pulses from a 1 kHz Ti:sapphire laser. THz pulse intensity as high as 200 MW/cm² was achieved. The energy conversion efficiency was 7 × 10⁻⁴. The capability of the present scheme to generate high energy shaped THz pulses was also demonstrated by using a sequence of optical pump pulses.     

Silicon donor and Stokes terahertz lasers

Two types of lasers based on hydrogen-like impurity-related transitions in bulk silicon operate at frequencies between 1 and 7 THz (wavelength range of 50-230 μm). These lasers operate under mid-infrared optical pumping of n-doped silicon crystals at low temperatures (<30 K). Dipole-allowed optical transitions between particular excited states of group-V substitutional donors are utilized in the first type of terahertz silicon lasers. These lasers have a gain ∼1-3 cm⁻¹ above the laser thresholds (>1 kW cm⁻²) and provide 10 ps-1 μs pulses with a few mW output power on discrete lines. Raman-type Stokes stimulated emission in the range 4.6-5.8 THz has been observed from silicon crystals doped by antimony and phosphorus donors when optically excited by radiation from a tunable infrared free electron laser. The scattering occurs on the 1s(E)→1s(A₁) donor electronic transition accompanied by an emission of the intervalley transverse acoustic g-phonon. The Stokes lasing has a peak power of a few tenths of a mW and a pulse width of a few ns. The Raman optical gain is about 7.4 cm GW⁻¹ and the optical threshold intensity is ∼100 kW cm⁻².     

Variable-temperature Raman scattering study on anatase titanium dioxide nanocrystals

The temperature dependence of the Raman modes in anatase TiO₂ nanocrystals has been investigated over the temperature range 77-873 K. With increasing temperature, the frequency of the E_g mode at 639 cm⁻¹ shifts sublinearly to the lower frequencies, however, the frequency of the lowest-frequency E_g mode shifts sublinearly to the higher frequencies from 138 cm⁻¹ at 77 K to 152 cm⁻¹ at 873 K and the frequency of the B_1g mode at 397 cm⁻¹ increases firstly and attains a maximum near 350 K. The linewidth of all of the three modes increases linearly with increasing temperature. The anharmonic effects contribute a lot to the temperature dependence behavior of the frequency and linewidth of Raman modes in anatase TiO₂ nanocrystals.     

Adsorption states of NO on the Pt(1 1 1) step surface

Using infrared reflection absorption spectroscopy (IRAS) and scanning tunneling microscopy (STM), we investigated the adsorption states of NO on the Pt(9 9 7) step surface. At 90 K, we observe three N-O stretching modes at 1490 cm⁻¹, 1631 cm⁻¹ and 1700 cm⁻¹ at 0.2 ML. The 1490 cm⁻¹ and 1700 cm⁻¹ peaks are assigned to NO molecules at fcc-hollow and on-top sites of the terrace, respectively. The 1631 cm⁻¹ peak is assigned to the step NO species. In the present STM results, we observed that NO molecules were adsorbed at the bridge sites of the step as well as fcc-hollow and on-top sites of the terrace. To help with our assignments, density functional theory calculations were also performed. The calculated results indicate that a bridge site of the step is the most stable adsorption site for NO, and its stretching frequency is 1607 cm⁻¹. The interactions between NO species at different sites on Pt(9 9 7) are also discussed.     

Empirical line parameters of methane from 1.1 to 2.1 μm

To provide line parameters for the near-infrared methane spectrum, 35,306 line positions and intensities at room temperature were retrieved between 6180 and 9200 cm⁻¹, along with 4936 lines between 4800 and 5500 cm⁻¹. For this, laboratory absorption spectra were recorded at 0.010-0.022 cm⁻¹ resolution using the McMath-Pierce Fourier Transform Spectrometer located on Kitt Peak in Arizona. Positions were calibrated using CO transitions at 2.3 and 1.6 μm and H₂O lines at 1.9 and 1.3 μm. The minimum line intensity included was 3.7×10⁻²⁶ cm⁻¹/(molecule cm⁻²), and the combined sum of the intensities in these two intervals was 7.085×10⁻²⁰ cm⁻¹/(molecule cm⁻²) at 296 (±4) K. Quantum assignments from the literature were matched for 1% of the features, and a new methane database was compiled for the near-infrared.     

ESR and optical study of Mn doped potassium hydrogen sulphate

The ESR spectrum of Mn²⁺ doped potassium hydrogen sulphate at liquid nitrogen temperature (77 K) has been analyzed and site of entered Mn²⁺ in the lattice has been discussed. The values of the zero field parameters that give good fit to the observed ESR spectra have been obtained. The obtained g, A, B, D, E and a values are 2.0002, 66×10⁻⁴ cm⁻¹, 26×10⁻⁴ cm⁻¹, 59×10⁻⁴ cm⁻¹, 32×10⁻⁴ cm⁻¹ and −8×10⁻⁴ cm⁻¹, respectively. The percentage of covalency of the metal-ligand bond has also been estimated. From the optical absorption study at room temperature, the distortion has been suggested. The observed bands are assigned as transitions from the ⁶A_1g(S) ground state to various excited quartet levels of Mn²⁺ ion in a cubic crystalline field. The electron repulsion and crystal field parameters B, C, Dq and α providing good fit to the observed optical spectra have been evaluated and the values obtained for the parameters are B=627 cm⁻¹, C=2580 cm⁻¹ , Dq=790 cm⁻¹ and α=76 cm⁻¹.     

Raman spectroscopy of SWNTs produced by a XeCl excimer laser ablation at high temperatures

Synthesis of single-wall carbon nanotubes (SWNTs) was carried out by an ablation method using a XeCl excimer laser. It was irradiated onto a graphite target containing Co and Ni at the temperatures of 1073, 1173, 1273, 1373, 1473, 1523 and 1623 K under the atmosphere (0.1 MPa) of Ar gas with the flow rate of 12 ml/min. The measurement by a scanning/transmission electron microscope and Raman spectroscopy found the formation of SWNTs with the diameter of about 1.3 nm and the length of about 2 μm in ablated carbonaceous soot. The ratio of peak intensity of 1590 cm⁻¹ (G band) to that of 1335 cm⁻¹ (D band) in the high frequency Raman spectra increased with increasing the ambient temperature. The radial breathing mode (RBM) in the low frequency Raman spectra shows that the mean diameter of SWNTs increased with increasing the ambient temperature.     

One-magnon light scattering and spin-reorientation transition in epitaxial BiFeO3 thin films

Raman scattering from one-magnon excitation has been observed for the first time in epitaxial BiFeO₃ thin films grown on (1 1 1) SrTiO₃ substrates. The intensities and the frequency of the magnon mode at 18.9 cm⁻¹ (M₁) showed a discrepancy at the characteristic temperatures of ∼140 and 200 K and the magnon mode at 27.9 cm⁻¹ (M₂) disappeared at ∼200 K suggesting spin-reorientation (SR) transition in the epitaxial BFO film. The dc susceptibility measurement showed a large discrepancy near these two temperatures evidently elucidating the spin-reorientation transition mechanism. The partial spectral weight of the magnon modes is believed to be transferred to the lowest phonon mode appearing at 72.8 cm⁻¹ and higher magnon mode M₂ disappearing near 200 K reveal magnon-phonon coupling near to SR transition.     

The influence of temperature on magnetic and microwave absorption properties of Fe/graphite oxide nanocomposites

Fe/graphite oxide nanocomposites were prepared by inserting Fe³⁺ into layers of graphite oxide and then reducing Fe³⁺/graphite oxide compound at different reduced reaction temperatures in H₂. The composition, crystal structure, magnetic and microwave absorption properties of Fe/graphite oxide nanocomposites were investigated using elemental analysis, transmission electron microscope (TEM), X-ray diffraction (XRD), magnetic hysteresis curve and electromagnetic parameter analysis. The results show that the densities of samples are 2.43–2.47 g/cm³ and the nanocomposites are soft magnetic materials. The optimum reduced reaction temperature for preparing Fe/graphite oxide nanocomposites is 600 °C. With the increase of the thickness of the sample, the matching frequency tends to shift to the lower frequency region, and theoretical reflection loss becomes less at the matching frequency. Microwave absorption property of Fe/graphite oxide nanocomposites prepared at 600  °C (FeGO600) is the best. When the thickness is 1 mm, the maximum theoretical reflection loss of FeGO600 is −9 dB and the frequency region in which the maximum reflection loss is more than −6.0 dB is 11–18 GHz. In conclusion, FeGO600 is a good candidate for microwave absorbent due to its low density, wide frequency region for microwave absorption and large reflection loss.     

Infrared spectra and stability of CO and H2O sorption over Ag-exchanged ZSM-5 zeolite: DFT study

The infrared spectra and stability of CO and H₂O sorption over Ag-exchanged ZSM-5 zeolite were investigated by using density function theory (DFT). The changes of NBO charge show that the electron transfers from CO molecule to the Ag⁺ cation to form an σ-bond, and it accompanies by the back donation of d-electrons from Ag⁺ cation to the CO (π*) orbital as one and two CO molecules are adsorbed on Ag-ZSM-5. The free energy changes ΔG, −5.55 kcal/mol and 6.52 kcal/mol for one and two CO molecules, illustrate that the Ag⁺(CO)₂ complex is unstable at the room temperature. The vibration frequency of C-O stretching of one CO molecule bonded to Ag⁺ ion at 2211 cm⁻¹ is in good agreement with the experimental results. The calculated C-O symmetric and antisymmetric stretching frequencies in the Ag⁺(CO)₂ complex shift to 2231 cm⁻¹ and 2205 cm⁻¹ when the second CO molecule is adsorbed. The calculated C-O stretching frequency in CO-Ag-ZSM-5-H₂O complex shifts to 2199 cm⁻¹, the symmetric and antisymmetric O-H stretching frequencies are 3390 cm⁻¹ and 3869 cm⁻¹, respectively. The Gibbs free energy change (ΔGH₂O) is −6.58 kcal/mol as a H₂O molecule is adsorbed on CO-Ag-ZSM-5 complex at 298 K. The results show that CO-Ag-ZSM-5-H₂O complex is more stable at room temperature.     

The high-resolution far-infrared spectrum of methane at the SOLEIL synchrotron

As a tetrahedral molecule, methane has no permanent dipole moment. Its spectrum, however, displays faint absorption lines in the THz region, due to centrifugal distorsion effects. This is important for planetary applications since this region is used to measure methane concentration in some planetary atmospheres, in particular on Titan. Up to now, all measurements relied either on some old low resolution infrared absorption spectra, or on high resolution Stark measurements for low J values only. Even if these results have been reexamined recently [Wishnow EH, Orton GS, Ozier I, Gush HP. The distorsion dipole rotational spectrum of CH₄: a low temperature far-infrared study. J Quant Spectrosc Radiat Transfer 2007;103:102-17], it seemed highly desirable to obtain much more precise laboratory data.The high-intensity synchrotron radiation, combined with a 151.75±0.1 m optical path in a White cell and a Bruker IFS 125 HR FTIR spectrometer at the AILES beamline of SOLEIL, enabled us to record this very weak spectrum at high resolution for the first time. Spectra were obtained in the 50-500 cm⁻¹ wavenumber range at 296 K and 9.91, 20, 50 and 100 mbar with a resolution of 0.00074, 0.00134, 0.0034 and 0.0067 cm⁻¹ (FWHM of the sinc function), respectively. The rotational clusters are fully resolved and the good signal-to-noise ratio has enabled precise measurements of transition intensities (92 cold band lines and 96 Dyad-Dyad hot band lines, with normal abundance intensities in the range 2×10⁻²⁶-1×10⁻²⁴ cm⁻¹/(mol cm⁻²)), yielding an accurate determination of the dipole moment derivatives. Such results should allow a better determination of CH₄ concentration in planetary objects.     

Preparation of pulse plated GaAs films

Thin GaAs films were prepared by pulse plating from an aqueous solution containing 0.20 M GaCl₃ and 0.15 M As₂O₃ at a pH of 2 and at room temperature. The current density was kept as 50 mA cm⁻² the duty cycle was varied in the range 10-50%. The films were deposited on titanium, nickel and tin oxide coated glass substrates. Films exhibited polycrystalline nature with peaks corresponding to single phase GaAs. Optical absorption measurements indicated a direct band gap of 1.40 eV. Photoelectrochemical cells were made using the films as photoelectrodes and graphite as counter electrode in 1 M polysulphide electrolyte. At 60 mW cm⁻² illumination, an open circuit voltage of 0.5 V and a short circuit current density of 5.0 mA cm⁻² were observed for the films deposited at a duty cycle of 50%.     

Luminescence studies on swift heavy ion irradiated nanocrystalline aluminum oxide

Pellets of nanocrystalline aluminum oxide synthesized by a combustion technique are irradiated with 120 MeV Au⁹⁺ ions for fluence in the range 5×10¹¹-1×10¹³ ions cm⁻². Two photoluminescence (PL) emissions, a prominent one with peak at ∼525 nm and a shoulder at ∼465 nm are observed in heat treated and Au⁹⁺ ion irradiated aluminum oxide. The 525 nm emission is attributed to F₂²⁺-centers. The PL intensity at 525 nm is found to increase with increase in ion fluence up to 1×10¹² ions cm⁻² and decreases beyond this fluence. Thermoluminescence (TL) of heat-treated and swift heavy ion (SHI) irradiated aluminum oxide gives a strong and broad TL glow with peak at ∼610 K along with a weak shoulder at 500 K. The TL intensity is found to increase with Au⁹⁺ ion fluence up to 1×10¹³ ions cm⁻² and decreases beyond this fluence.     

Magnetic and electrical properties of amorphous Ge1−xCrx thin films grown by low temperature vapor deposition

Amorphous Ge_1−xCr_x thin films are deposited on (1 0 0)Si by using a thermal evaporator. Amorphous phase is obtained when Cr concentration is lower than 30.7 at%. The electrical resistivities are 1.89×10⁻³–0.96×10² Ω cm at 300 K, and decrease with Cr concentration. The Ge_1−xCr_x thin films are p-type. The hole concentrations are 5×10¹⁶–7×10²¹ cm⁻³ at 300 K, and increase with Cr concentration. Magnetizations are 7.60–1.57 emu/cm³ at 5 K in the applied field of 2 T. The magnetizations decrease with Cr concentration and temperature. Magnetization characteristics show that the Ge_1−xCr_x thin films are paramagnetic.     

The absorption spectrum of phosphine (PH3) between 2.8 and 3.7 μm: Line positions, intensities, and assignments

Over 8000 line positions and intensities of phosphine (PH₃) at 3 μm have been measured at 0.0115 cm⁻¹ resolution with the McMath-Pierce Fourier Transform spectrometer at Kitt Peak. The observed line intensities ranged from 4.13 × 10⁻⁶ to 4.69 × 10⁻² cm⁻² atm⁻¹ at 296 K, for line positions between 2724.477 and 3601.652 cm⁻¹. This region spans eight interacting vibrational states: 3ν₂ (2940.8 cm⁻¹), 2ν₂ + ν₄ (3085.6 cm⁻¹), ν₂ + 2ν₄ (3214.9 cm⁻¹), ν₁ + ν₂ (3307.6 cm⁻¹), ν₂ + ν₃ (3310.5 cm⁻¹), 3ν₄ (∼3345 cm⁻¹), ν₁ + ν₄ (3426.9 cm⁻¹), and ν₃ + ν₄ (3432.9 cm⁻¹). Assignments have been determined for all the bands except 3ν₄ (a weak band in a highly congested area) for a total of 4232 transitions. The total integrated intensity for this region is 5.70 cm⁻² atm⁻¹ near 296 K, and assigned lines account for 79% of the observed absorption. The two strongest bands in the region are ν₁ + ν₄ and ν₃ + ν₄ with band strengths at 296 K of 1.61 and 2.01 cm⁻² atm⁻¹, respectively. An empirical database of PH₃ line parameters (positions, intensities, and assignments) is now available. Lower state energies (corresponding to assignments from this study) and line widths from the literature are included; default values are used for unassigned features.     

Phase transformation of graphite irradiated by high-intensity pulsed ion beams

The microstructure and morphology of graphite irradiated by high-intensity pulsed ion beams (HIPIB) has been studied by varying the ion current density as 200, 350 and 1500 A/cm² with one to five shots. Phase transformation from graphite to diamond-like carbon (DLC) on the HIPIB-irradiated graphite was confirmed by Raman spectroscopy where a typical broadened asymmetric peak appeared in the wavenumber range of 1100-1700 cm⁻¹. Formation of DLC on the irradiated graphite strongly depended on the HIPIB parameters and preferably took place at the medium ion current density of 350 A/cm² up to five shots. Numerical simulation of ablation process was performed to explore the transformation mechanism of DLC from graphite irradiated by HIPIB. The calculation showed that the temperature profile in irradiated graphite at 350 A/cm² is almost identical to that at 200 A/cm², showing a deeper heat-affected zone in comparison with that of 1500 A/cm². Moreover, the ablation depth per shot is around 0.8 μm at 350 A/cm², higher than that of 0.4 μm at 200 A/cm² and much lower than that of 8.4 μm at 1500 A/cm², respectively. The experimental and numerical results indicate that a proper temperature and pressure repetitively created in the top layer of ablated graphite during HIPIB irradiation facilitates the phase transformation.     

Line mixing effects in the ν2 + ν3 band of methane

This study provides the first direct experimental measurements of the off-diagonal relaxation matrix element coefficients for line mixing in air-broadened methane spectra for any vibrational band and the first off diagonal relaxation matrix elements associated with line mixing for pure methane in the ν₂ + ν₃ band of ¹²CH₄. The speed-dependent Voigt profile with line mixing is used with a multispectrum nonlinear least squares curve fitting technique to retrieve the various line parameters from 11 self-broadened and 10 air-broadened spectra simultaneously. The room temperature spectra analyzed in this work are recorded at 0.011 cm⁻¹ resolution with the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory, Kitt Peak, Arizona. The off-diagonal relaxation matrix element coefficients of ν₂ + ν₃ transitions between 4410 and 4629 cm⁻¹ are reported for eighteen pairs with upper state J values between 2 and 11. The observed line mixing coefficients for self broadening vary from 0.0019 to 0.0390 cm⁻¹ atm⁻¹ at 296 K. The measured line mixing coefficients for air broadening vary from 0.0005 to 0.0205 cm⁻¹ atm⁻¹ at 296 K.     

Experimental low energy values of CH4 transitions near 1.33 μm by absorption spectroscopy at 81 K

The high resolution absorption spectrum of methane has been recorded at liquid nitrogen temperature by direct absorption spectroscopy between 1.36 and 1.30 μm (7351-7655 cm⁻¹) using a cryogenic cell and a series of distributed feed back (DFB) diode lasers. The investigated spectral range corresponds to the high energy part of the icosad dominated by the ν₂+2ν₃ band near 7510 cm⁻¹. The positions and strengths at 81 K of 3473 transitions were obtained from the spectrum analysis. The minimum value of the measured line intensities (at 81 K) is on the order of 10⁻²⁶ cm/molecule, i.e. significantly lower than the intensity cut off of the HITRAN database in the region (4×10⁻²⁵ cm/molecule at 296 K). From the variation of the line strength between 81 and 296 K, the low energy values of 1273 transitions could be determined. They represent 69% and 81% of the absorbance in the region at 296 and 81 K, respectively. The obtained results are discussed in relation with the few rovibrational assignments previously reported in the region.