Efficient production of13C2F4 in the infrared laser photolysis of CHClF2

We report the isotopically selective decomposition of chlorodifluoromethane. Chlorodifluoromethane is used industrially in high volume for the production of tetrafluoroethylene and its polymers; thereby it is an attractive working substrate for a medium scale isotope separation process, both in terms of its price and availability.We have studied the infrared multiphoton decomposition of carbon-13 substituted chlorodifluoromethane molecules present at their natural abundance (1.11%). A well defined CO₂ laser pulse (80 ns FWHM) was used and both the yield of carbon-13 enriched product and the net absorption of laser radiation were measured. These measurements were made as a function of substrate pressure (10-800 Torr), CO₂ laser line (9P 12–9P 32) and fluence (2–8 J cm^–2) and were used to determine the energy expenditure per carbon atom produced () at specified product carbon-13 content in the range 30%–96%. The results of these parametric studies were interpreted in terms of the kinetics of multiphoton absorption and dissociation, and allowed an initial optimization of the experimental conditions to minimize .Optimum results were obtained at 1046.9 cm^–1, 69 cm^–1 to the red of the¹²CHClF₂ v ₉ band center. Irradiation of 100 Torr of chlorodifluoromethane at 3.5 J cm^–2 gave tetrafluoroethylene containing 50% carbon-13 for an absorption of 140 photons (0.017 keV) per carbon atom produced. This efficiency compares favourably with existing carbon-13 enrichment technologies and would require an absorption pathlength of only 2 m to absorb half the incident photons.Issued as NRCC 20112     

Absorption of subpicosecond ultraviolet laser pulses in high-density plasma

The absorption of 250 fs KrF laser pulses incident on solid targets of aluminum, copper and gold has been measured for normal incidence as a function of laser intensity in the range of 10¹²–10¹⁴ W cm^–2 and as a function of polarization and angle of incidence for the intensity range of 10¹⁴–2.5×10¹⁵ W cm^–2. As the intensity increases from 10¹² W cm^–2 the reflectivity at normal incidence changes from the low-intensity mirror reflectivity value to values in the range of 0.5–0.61 at 10¹⁴ W cm^–2. For this intensity maximum absorption of 63–80% has been observed for p-polarized radiation at angles of incidence in the range of 54°–57°, increasing with atomic number. The results are compared with the expected Fresnel reflectivity from a sharp vacuum-plasma interface with the refractive index given by the Drude model and also to numerical calculations of reflectivity for various scale length density profiles. Qualitative agreement is found with the Fresnel/Drude model and quantitative agreement is noticed with the numerical calculations of absorption on a steep density profile with normalized collision frequencies, v/, in the range of 0.13–0.15 at critical density and normalized density gradient scale lengths, L/₀, in the range of 0.018–0.053 for a laser intensity of 10¹⁴ W cm^–2.At 2.5×10¹⁵ W cm^–2 a small amount of preplasma is present and maximum absorption of 64–76% has been observed for p-polarized radiation at angles of incidence in the range of 45°–50°.Dedicated to Prof. Dr. Rudolf Wienecke on the occasion of his 65^th birthdayOn leave from: Department of Electrical Engineering, University of Alberta, Edmonton, T6G 2G7, Canada     

Estimation of the Optimum Concentration Interval of the Contents of Praseodymium, Neodymium, Europium, Holmium, and Erbium in a Solution

Based on the electronic absorption spectra of Pr³⁺, Nd³⁺, Eu³⁺, Ho³⁺, and Er³⁺ ions in 1 M aqueous solutions of chloric acid, calibration graphs have been constructed in a concentration of metals–optical density of a solution format for different frequencies. The band for praseodymium was used at 22,520 cm^–1, for neodymium at 17,380, 13,480, and 12,560 cm^–1, for europium at 25,380 cm^–1, for holmium at 18,580 and 15,580 cm^–1, and for erbium at 39,160, 26,480, and 19,160 cm^–1. The errors in determining the concentration of the indicated elements as a function of their content have been calculated. It is shown that for perchloric solutions of praseodymium it is possible to correctly determine its contents within the concentration range 0.1–1.5% at a frequency of 22,520 cm^–1; for neodymium the ranges are 0.4–1.0, 0.3–1.0, and 0.5–1.0% at 17,380, 13,480, and 12,560 cm^–1, respectively; for europium 0.4–1.5% at 25,380 cm^–1; for holmium — 0.2–1.5 and 0.4–1.5% at 15,580 and 18,580 cm^–1, and for erbium the range is 0.4–1.0% at frequencies of 39,160, 26,480, and 19,160 cm^–1.     

FTIR and Raman spectroscopic study of Fenugreek (<Emphasis Type="Italic">Trigonella foenum graecum L.</Emphasis>) seeds

The composition of Fenugreek seeds in the form of powder, ash, and oil is investigated through FTIR and FT Raman spectra measurements. The results indicate that Fenugreek seeds (powder) are rich in proteins. Fats (lipids) and starch are present in small amounts in the seeds. The FTIR absorption bands of seed powder appeared at: 3365 cm^–1 assigned as N-H stretching vibrations (amide A of protein), 1657 cm^–1 (C=O, amide I), 1540 cm^–1 (N-H bending vibration, amide II), and 1240 cm^–1 (N-H bending, amide III). In the FT Raman spectra the band at 1661 cm^–1 is ascribed to amide I (C=O) of proteins while the band at 1080 cm^–1 indicates the starch. The fenugreek oil Fourier transform infrared absorbance ratios A(3009 cm^–1)/A(2924 cm^–1), A(3009 cm^–1)/A(2854 cm^–1), and A(3009 cm^–1)/A(1740 cm^–1) were considered for measuring the iodine values. These ratios (0.3609, 0.4916, and 0.4129) revealed that the iodine value of fenugreek oil is higher than that of other oils. On the other hand, the ash of fenugreek is very rich in phosphate compounds. The spectra showed absorption bands at frequencies 1082, 1000, 618, and 566 cm^–1, and the FT Raman spectrum showed a strong absorbance band at 793 cm^–1, which is due to phosphate compounds. It could be concluded that the inorganic part of fenugreek consists mainly of phosphate compounds. The Fenugreek seed contains proteins, fat, fiber, and ash, which is in complete harmony with AACC, 1980.__________Published in Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 106–110, January–February, 2005.     

Cross section of supercooled238UF6 in multiphoton absorption induced by 16 micrometer Raman-laser radiation

Measurements of multiphoton absorption of 16 µm Raman-laser radiation in supercooled²³⁸UF₆ at 90 K were performed by using a pulsed Laval nozzle with an optical path length of 50 cm. The laser fluence was varied between 50 and 500 mJ/cm² for four frequencies in the range from 625 to 629 cm^–1. The energy absorbed by²³⁸UF₆ molecules was investigated as a function of laser frequency or fluence, and highly accurate results were obtained with the use of the nozzle whose optical path length is much greater than that of nozzles used before. The results indicated that the absorption cross section at the peak absorption frequency (627.8cm^–1) was proportional to the –1/3 power of the fluence.     

Fourier transform measurements of SO2 absorption cross sections: II.: Temperature dependence in the 29 000–44 000 cm (227–345 nm) region

This paper is the second of a series that reports results on the measurements of the absorption cross section of SO₂ in the UV/visible region at high resolution and that investigates high temperatures in support to planetary applications. Absorption cross sections of SO₂ have been obtained in the 29 000–44 000 cm⁻¹ spectral range (227–345 nm) with a Fourier transform spectrometer at a resolution of 2 cm⁻¹ (0.4500 cm MOPD and boxcar apodisation). Pure SO₂ samples were used and measurements were performed at room temperature (298 K) as well as at 318, 338 and 358 K. Temperature effects in this spectral region are investigated and are favorably compared to existing studies in the literature. Comparison of the absorption cross section at room temperature shows good agreement in intensity with most of the literature data, but shows that most of the latter suffer from inaccurate wavelength scale definition. Moreover, literature data are often given only on restricted spectral intervals. Combined with the data described in the first part of this series of papers on SO₂, this new data set offers the considerable advantage of covering the large spectral interval extending from 24 000 to 44 000 cm⁻¹ (227–420 nm), at the four temperatures investigated.     

Low-Temperature Midinfrared Absorption in GaSe

We report the measurement of the temperature dependence of the absorption spectra of - GaSe over the temperature range 300 K to 5 K. Measurements have been made for both the e-ray (polarized parallel to the crystals c-axis) and the o-ray (polarized perpendicular to the c-axis), over the spectral range 4000 to 10 cm^–1. Nine absorption lines at 417, 440, 499, 546, 891, 945, 1015, 1093, 1270 cm^–1 were recorded at 300 K for the e- ray spectra. Some of these lines were identified using the results of a modified single layer, linear chain model of GaSe. The lines at 417, 440 and 499 cm^–1 were assigned to local impurity absorption originating from N, Mg and O, respectively. The weak lines at 945, 1015 and 1093 cm^–1 were assigned to hole transitions from the acceptor levels to the top of the valence band. Two absorption lines at 891 cm^–1 and 1270 cm^–1 were assigned to hole transitions from the quasi-local acceptor levels to the double degenerate valence sub-bands ₅ or ₆. The origin of lines recorded in the far IR absorption spectra at 20, 37 cm^–1 and 362 cm^–1 were also identified.     

Electronic absorption in silicate mineral of copper

The electronic absorption spectrum of chrysocolla, a silicate mineral of copper, has been studied at room and liquid air temperatures. The observed bands were satisfactorily explained as belonging to Cu²⁺ ion subjected to tetragonal and spin-orbit fields. A good fit between the theoretical and observed band positions was obtained for the following crystal field parameters:Dq=–1400 cm^–1 Ds=–3000 cm^–1 Dt=–800 cm^–1 =–800 cm^–1     

Determination of the gap distribution in YBa2Cu3O7 using a far-infrared reflection-Fabry-Pérot device

This paper reports on far-infrared measurements of YBa₂Cu₃O₇ films oriented with the c-axis perpendicular to the surface, by using a silicon reflection Fabry-Pérot interferometer as a multireflection device. From these we could derive the dielectric function, the refractive index, the field penetration depth and the surface impedance of the material. The one order of magnitude higher sensitivity of the method compared to a direct reflectance measurement allowed to find an almost continuous gap distribution in the 70–215 cm^–1 region together with a separate gap at about 330 cm^–1. A quasizero gap absorption is found down to 20 cm^–1 even at low temperatures (10 K).     

Luminescence of rare gas crystals at high excitation densities for VUV laser applications

Exciton densities of the order of 10¹⁸ cm^–3 are generated in 0.1–0.3 mm thick surface layers in an area of 10×20 mm² of optically clear rare gas crystals. The quantum efficiencies at 126 nm (Ar), 145 nm (Kr), and 172 nm (Xe) remain near 0.5 even for the highest excitation densities. The corresponding gain coefficients of 2.6 cm^–1 (Ar) to 18 cm^–1 (Xe) exceed those of high pressure gas lasers by a factor of 20. Stimulated emission is inferred by observing the line narrowing, the dependence of intensities and time courses on excitation density and amplification measurements. The net gain coefficient is reduced however to 0.5–1 cm^–1 by transient absorption of excited centers and scattering by irradiation induced defects. The results are analysed by a system of rate equations for the excitation, relaxation, quenching, and amplification processes. A peculiar temperature dependence of the quantum efficiencies and time courses is attributed to electron trapping at grain boundaries.     

The UV absorption spectrum of the phenyl radical isolated in solid argon

Phenyl radicals have been generated by photodecomposition of nitrosobenzene isolated in solid argon at 12 K. In this medium the origin of the first UV absorption band of nitrosobenzene corresponding to theS ₀ S ₂ transition is found at 30260 cm^–1. Excitation with an excess energy of 2200 cm^–1 results in very efficient photodissociation. The fragments NO and phenyl are stable for many hours. Annealing of the sample above 35 K led to partial recombination and recovery of the absorption spectrum of nitrosobenzene. The UV spectrum of the phenyl radical was obtained in the wavenumber range 25000–45000 cm^–1, apparently without contamination by other species. It shows sharp lines at 25220, 33880, and 34820 cm^–1 and two broader maxima at 38360 and 41060 cm^–1. Of these only the line at 34820 cm^–1 had been assigned to the phenyl radical in earlier work. These data are compared to recent molecular orbital calculations.Dedicated to Prof. F. P. Schäfer on the occasion of his 65th birthday.     

Optical studies on free-standing polypyrrole films by the photopyroelectric method

Optical spectra of free-standing polypyrrole films were investigated by a novel PhotoPyroElectric (PPE) method. The reflection and absorption spectra in the range 2000–25000 cm^–1 of TsO^–- and ClO ₄ ^su– -doped polypyrrole films were obtained with an experimental setup comprising two pyroelectric sensors. The absorption bands due to electronic transitions to the bonding and antibonding bipolaronic levels appear at 11 000 and 21 500 cm^–1, respectively. Some relevant details in the polypyrrole spectrum in the 2000–5000 cm^–1 range were observed. The absorption band located at 3400 cm^–1 is characteristic for NH stretching vibration. The bands in the 2300–2500 cm^–1 range are ascribed to the vibration of N⁺H groups containing positively charged nitrogen. The PPE spectra also reveal changes of the electronic and vibrational absorption bands after polymer reduction and HCl treatment.     

Design of multiple layered a-Si:H(F)/a-SiGex:H(F) films for enhancement in photoresponse in the near-infrared spectrum

Photo-electric properties of a-Si:H(F)/a-SiGe_x:H(F) multilayer films were investigated by measurements of optical absorption, and photoconductivity in both steady and transient modes with the repetition length and the difference in the optical gap between a-Si:H(F) and a-SiGe_x:H(F) as the variables. Measurements of primary photocurrent clarified that photosensitivity for the multilayer films extended to longer wavelengths of around 725 nm, while high resistivity was maintained despite of lowering the band gap.The drift mobility of electrons was measured by the time-of-flight technique, showing 10^–2-10^–3 cm²/Vs, while the drift mobility-lifetime products of electron was maintained to be 10^–7 cm²/V. On the other hand, the drift mobility of holes was 10^–3 cm²/Vs, which was the similar magnitude to that of a-Si:H(F).     

Transient absorption and laser output of YAG : Nd

YAG : Nd grown under 98% Ar 2% H₂ protective atmosphere free of nitrogen or hydrocarbons showed after UV irradiation broad absorption peaked at 1·9×10⁴ cm^–1 which disappeared relatively slowly at room temperature. It was more intensive in oxygen treated samples than in those annealed in hydrogsn. Transient absorption suppresses laser output by the increase of absorption at 0·94×10⁴ cm^–1 (1064 nm) and, particularly in CW mode, by the anomalous rod deformation. YAG : Nd containing Fe ions (2·10^–4 wt%) showed no transient absorption.     

Intersubband absorption in highly photoexcited semiconductor quantum wells

Transient mid infrared (MIR) absorption spectroscopy is used to investigate transitions between higher electronic subbands in semiconductor quantum well (QW) structures after interband photoexcitation with intense picosecond pulses in the visible spectral range. Our investigation focuses on the e₂–e₃ intersubband transition in an asymmetric undoped GaAs/AlGaAs QW structure. At an injected nonequilibrium carrier density of 1×10¹³ cm⁻²/QW, an e₂–e₃ absorption band at 99 meV with a spectral width of 5 meV is found. For a higher density studied, 3×10¹³ cm⁻²/QW, the band is broadened and blueshifted by 30 meV. Intersubband absorption signals are distinguished from free-carrier absorption signals in the MIR by their characteristic time behavior.     

Xe2Cl fluorescence and absorption in self-sustained discharge XeCl lasers

Fluorescence at 490 nm from the triatomic excimer Xe₂Cl^* has been investigated to determine the 308 nm absorption due to this species in an x-ray preionized, self-sustained gas discharge XeCl laser. The dependence of Xe₂Cl^* density on laser intensity (at 308 nm), buffer gas and Xe and HCl partial pressures has been determined for discharges with a peak electrical power deposition of 2.5 GWl^–1. Xe₂Cl^* absorption is estimated to reach 0.6% cm^–1 under non-lasing conditions but decreases to a non-saturable 0.2% cm^–1 for intracavity laser intensity>1 MW cm^–2. XeCl^* and Xe₂Cl^* fluorescence intensities were found to be a similar for both helium and neon buffer gases but laser output was a factor of two greater with a neon buffer.     

Infrared spectra of urine from cancerous bladders

The infrared spectra of organic constituents of urine from cancerous bladders of some patients were recorded. The spectra of the organic part of the samples were classified into five types according to the bulk constituents. Samples with type A spectra consisted mainly of proteins with only trace amounts of lipids. Their spectra were characterized mainly by the absorption bands of proteins at the frequencies 3330, 3075, 2960, 2850, 1650, 1530, 1450, 1400 and 1320 cm^–1, in addition to a weak band at 1720 cm^–1 due to the absorption of lipids. Samples with type B spectra were characterized by high amounts of proteins and low amounts of lipids and phosphate compounds. The presence of phosphate compounds was indicated by the absorption bands at the frequencies 1100 and 1030 cm^–1. Samples giving spectral type C were characterized by high urea contents as indicated by the presence of two strong bands at 1670 and 1630 cm^–1. Samples with the spectral type D consisted of urea and phosphate compounds whereas the last spectral type E consisted mainly of calcium oxalates, uric acids and phosphate compounds. The presence of calcium oxalates was indicated by the presence of its diagnostic bands at the frequencies 1630 and 1330 cm^–1, while the presence of uric acid was indicated by the bands at the frequencies 1360, 1130, 1020 and 880 cm^–1. On the other hand, the spectra of the organic part of urine from some normal bladders exhibited the characteristic bands of urea only.Careful examination of the spectra of the inorganic part of urine revealed that some samples consisted mainly of hydroxyapatite. The absorption bands of hydroxyapatite appeared at the frequencies 568, 603, 985, 1037 and 1128 cm^–1. The spectra of other samples showed that the bands of basic phosphates at the frequencies 568, 620, 727, 890, 1035 and 1140 cm^–1. The spectra of the inorganic part of urine from a number of normal bladders displayed the bands of basic phosphates. The relationship between urine constituents and pathological types of bladder tumor tissue was discussed.     

Absorption spectrum of nitrous acid for the ν1+2ν3 band studied with continuous-wave cavity ring-down spectroscopy and theoretical calculations

We present the high resolution absorption measurements of gaseous HONO at room temperature using continuous-wave cavity ring-down spectroscopy in the near-infrared region between 6017 and 6067 cm⁻¹ at a resolution of 1 pm (0.037 cm⁻¹). For the trans-HONO isomer an extensive analysis of the ν₁+2ν₃ combination band 6045.8089 cm^–1 was performed starting from the results of a previous study for the 1¹ and 3¹ vibrational states [Guilmot J-M, Godefroid M, Herman M. Rovibrational parameters for trans-nitrous acid. J Mol Spectrosc 1993;160:387–400]. The present combination band is perturbed because of the existence of several dark states of HONO which could not be identified unambiguously. The rotational constants achieved for the 1¹3² state deviate slightly from the values which are predicted from the rotational constants achieved in the previous studies for the 1¹ and 3¹ vibrational states of trans-HONO.     

High resolution molecular spectroscopy in the submillimeter region

Fourier Transform laboratory measurements have been carried out, for the first time in the 8–85 cm^–1 spectral region, with an unapodized resolution of 3.3. 10^–3 cm^–1 and a frequency accuracy of 2. 10^–4 cm^–1. Samples from spectra of several molecules namely: CO, O₃, H₂O₂, NO, NO₂, HNO₃, SO₂, H₂S, HOCL, NOCL, HNCO, ND₃ and AsH₃ are presented to show both the quality of the measurements and the type of information supplied by high resolution spectroscopy in the submillimeter region.