Infrared laser stark shift spectroscopy in ammonia

The Stark effect in ammonia has been theoretically and experimentally analyzed using lead salt tunable diode laser absorption spectroscopy and CO₂ laser absorption spectroscopy of several absorption lines around 1050 cm^–1 applied to an all-optical sensor for measuring of electric field strength. Measurements of the Stark splitting effect of theaR(5,K) ammonia lines forK=1–5 as well as for the sR(3,K) lines forK=0–3 have been made at Doppler broadening pressures and for several different electric field strengths. Theoretical electric field dependent energy levels have been evaluated by diagonalization of a 6×6 energy matrix constructed using both electric field independent and dependent terms. From the theoretical analysis the resolution can be predicted and optimized both in the Doppler broadened and in the pressure broadened regimes. The predicted resolution is 0.5% at an electric field strength of 20 kV/cm. The theoretical calculations and the experimental data recorded with the tunable diode laser system were compared with independent measurements made with a CO₂ laser system. The agreement between experimentally recorded and theoretically calculated spectra is good which indicates that the theoretical model is satisfactory for our purposes. The contribution from the normally forbidden ssR(5, 3) ammonia line to the absorption at theP(12) CO₂ laser line in the 9 m band is briefly discussed.     

The applications of the stark effect to the stabilization of the CO2 laser and the submillimeter laser

Methods based on the Stark effect are described for dither-free frequency stabilization of the optically pumped submm laser. The CO₂ pump laser was stabilized using a Stark Lamb dip signal of the submm lasant in an external Stark cell. An estimated frequency stability (f/f) better than ±1.4×10^–8, for one hour recording, was obtained by this method. The frequency of the submm laser was stabilized using the d.c. and a.c. Stark effects for a metal-dielectric rectangular waveguide laser. An estimated frequency stability of ±6×10^–8 was obtained for 119 m line of CH₃OH laser for one hour recording.     

Submillimeter laser action of CW optically pumped CF2Cl2 (Fluorocarbon 12)

Eleven new CW far infrared (FIR) laser lines have been observed in the 600 m–1200 m range from the CF₂Cl₂ (Fluorocarbon 12) molecule optically pumped by a CO₂ laser. A 510^–4–10^–3 accuracy is achieved in the measurement of the FIR wavelengths.The frequency offset between the CO₂ pump center and the absorption line centers are measured using the transferred Lamb dip technique. Owing to a recent spectroscopic study of the CF₂ ³⁵Cl₂ molecule three lines may be assigned with great confidence as rotational transitions in thev ₆ vibrational band 923 cm^–1 of this main isotope.     

New CW FIR laser lines obtained in ammonia pumped by a CO2 laser, using the Stark tuning method

We report fifty seven CW FIR emissions observed in NH₃, by resonant pumping with a CO₂ laser. Exact coincidences between IR absorption lines of the gas and emission lines of the CO₂ laser have been carried out by Stark tuning. IR frequency shifts, up to 30 GHz, have allowed the pumping of forty three NH₃ transitions.These FIR emissions correspond to thirty one different wavelengths in the 50–400 m range; eighteen ones of them are new emitted wavelengths by pumping with the CO₂ laser.     

Double resonance and collision-induced transitions in the radiofrequency spectra of H2CO and HDCO observed inside the cavity of a CO2 laser

Many radiofrequency resonances corresponding to transitions between the two components of a K-type doublet in H₂CO and HDCO have been observed using infrared-radiofrequency double resonance inside a CO₂ laser cavity. For strong resonances, additional transitions induced by collisions have also been observed and these provide information on collisional processes. The collision-induced transitions also provide a method for assigning the K doublet frequencies in the ground and v₄ = 1 states of H₂CO, and in the ground, v₅ = 1, and v₆ = 1 states of HDCO; the rovibrational transitions pumped by the CO₂ laser can therefore be determined. The upper state rotational transitions and the infrared frequencies for the transitions in exact coincidence with the CO₂ laser lines provide accurate additional data in the analysis of the conventional infrared spectrum of the ν₅ and ν₆ bands of HDCO. In addition, the 195-μm far-infrared laser line in HDCO, observed by Dangoisse et al. [J. Quantum Electron. QE-13, 730–731 (1977)] has been assigned as the 24_6,19→23_6,18 transition in the v₆ = 1 state.     

Thev2 andv5 bands of CD3Cl: Infrared spectra and stark patterns with hyperfine structure

Infrared spectra of theV ₂ andV ₅ bands of CD₃Cl have been recorded with a resolution of about 0.015 cm^–1 and assigned. Moreover Stark patterns of the trideuterated methyl chloride for two CO₂ laser lines with saturated Lamb dips have been analysed. Many new strong coincidences showing hyperfine structure are observed and assigned.     

Acoustooptic extension of the frequency tunability of CW CO2 lasers: New FIR lasers emissions from CH3OH and13CH3OH

We have increased the frequency tunability of our CW waveguide CO₂ lasers by means of an acoustooptic amplitude modulator, operating at the fixed frequency of 90 MHz. The up-shifted, or down-shifted, laser optical sideband can be generated independently by adjusting the orientation of the modulator. The efficiency is larger than 50%. The frequency tunability of the CO₂ laser around each laser line is thus increased by 180 MHz. To demonstrate the possibilities of this method, a source composed of the above modulator and of a CW, 300 MHz tunable waveguide CO₂ laser has been used for the search of new large offset FIR laser lines from optically pumped CH₃OH and¹³CH₃OH molecules. As a result 15 and 10 new large offset laser lines were discovered respectively. New assignments of some laser lines are also proposed. We have also measured the Stark effect, the offset, and the polarization of other already known lines. In particular a Stark effect frequency tuning of about 1 GHz is demonstrated for a laser line at 208.399 m.     

FIR Stark spectroscopy on optically pumped CH3OH laser

An extensive theoretical and experimental analysis of the absorption and emission spectrum of a CH₃OH FIR-laser excited by a conventional CO₂ laser is presented. Particular interest is devoted to the Stark shifts of the pump and lasing lines and to the electric field dependence of the Fir-laser output of the various lines. The offsets with respect to the exciting radiation and the Stark shifts of the IR absorption (pump) lines are measured by means of the transferred Lamb dip technique. The theoretical behaviours of the Stark patterns are calculated for several choices of the quantum numbers and selection rules involved in the transitions. A large variety of experimental results are reported and compared to theory. Non-linear Stark shifts have been observed for the 37.5m FIR laser line and for the IR-pump transitions excited by the 9-P(38) and 10-R(38) CO₂ laser Lines. Line assignments are proposed and new FIR laser lines are reported.     

Infrared absorption of silane,ammonia, acetylene and diborane in the range of the CO2 laser emission lines: Measurements and modelling

Absorption spectra of the gases SiH₄, NH₃, C₂H₂ and of SiH₄/Ar and SiH₄/B₂H₆ mixtures have been measured in the spectral range of the CO₂ laser from 9.2 to 10.8 µm. In agreement with literature, silane shows the highest absorption (absorption coefficient = 3.3 × 10^–2 Pa^–1 m^–1). The deviation of the measured absorption behaviour of silane from literature, as far as the pressure dependence is concerned, can be explained by the enhanced spectral energy density in our experiment. This is confirmed by a rate-equation model involving the basic mechanisms of V-V and V-T energy transfer between vibrationally excited silane molecules. In contrast to silane, the absorption coefficient of NH₃ at the 10P(20) laser line is 4.5 × 10^–4 Pa^–1 m^–1 atp = 20 kPa and has its maximum of 4.5 × 10^–3 Pa^–1 m^–1 at the 10R(6) laser line. For C₂H₂ and B₂H₆, is even less ( 2.1 Ò 10^–5 Pa^–1 m^–1 for C₂H₂).     

R branch tuning characteristics of the13CH3F Raman FIR laser

Summary We described a¹³CH₃F Raman laser pumped by a grating tuned 20 atmospheres CO₂ laser. The emission characteristics of the¹³CH₃F laser extends from 14 cm^–1–35 cm^–1 and from 49 cm^–1–72 cm^–1; about 65% of these frequency ranges can be covered with tunable radiation. The characteristics shows a strong dependence on the rotaional quantum numbers of the states involved in the Raman laser transitions and, within each tuning interval, on the frequency offset with respect to the frequencies of resonant transitions. We obtained, at 51 cm^–1, a maximum FIR laser pulse energy of about 800 J (at a pump energy of 200 mJ), corresponding to a photon conversion of about 8%. In some cases we have observed simultaneous emission at a Raman and a cascade frequency. In addition, FIR emission power dependence on¹³CH₃F gas pressure and pump pulse power were investigated for different J quantum numbers.     

Submillimeter emission lines from CD2Cl2 optically pumped lasers

Fifty-five new submillimeter laser lines from optically pumped CD₂Cl₂, have been obtained in a FIR metallic waveguide resonator. Twenty-seven lines, ranging from 184 m to 1387 m, and twenty-eight lines, from 219 m to 888 m, have been observed when using CW CO₂ laser and CW N₂O laser optical pumping, respectively. The accuracy of wavelength measurements are of the order of 3.10^–3.     

13CH3OH and13CD3OH optically pumped fir laser: New large offset emission and optoacoustic spectroscopy

27 new, large offset, FIR laser lines from¹³CH₃OH and one from¹³CD₃OH have been discovered by pumping with a high tunability waveguide CW CO₂ laser. Optoacoustic measurements of isotopic methyl alcohol have also been performed and the pump offsets of the new and of previously known lines have been measured and checked. Frequency tunability by Stark effect has been observed for 6 strong lines. Some assignments are discussed.     

Determination of the Concentration of Electrons in the Laser Plasma of Helium

The dependence of the Stark width of the spectral line of He II P 468.6 nm on the electron concentration in the laser plasma of helium for the range of electron densities N _e = (1–10)·10²³ m^–3 and electron temperatures of the order of 60 kK has been measured. The results obtained correspond well to Griem's theoretical data. An empirical relation is suggested which makes it possible to reliably determine the electron concentration from measured halfwidths in the investigated range of N _e.     

Accurate determination of wavenumbers for iodine molecular lines in the red spectral region

The hyperfine structure of various absorption lines of molecular iodine with wavenumbers between 12980 and 13890 cm^–1 has been resolved using Doppler-free polarization spectroscopy. The wavenumbers of theo-component of 17 rovibrational lines of I₂ due to the transitionB ³ _ou ⁺ –X¹ _g ⁺ with even rotational quantum numbers have been determined with an accuracy of 0.001 cm^–1. A comparison of the centers of gravity of these 17 lines with the values of the iodine atlas of Gerstenkorn et al. yields a difference of thus corroborating the data of the iodine atlas in the red region within limits of error.     

Assignments of optically pumped CD3OH laser lines

Six FIR laser lines from CD₃OH pumped by the 10R(36) and the 10R(18) CO₂ laser lines are assigned to specific rotational energy levels in the excited C–0 stretch state. It is found that their upper laser levels are shifted by a Fermi resonance between the C–0 stretch vibration and the third and forth harmonics of the torsional mode. The Fermi resonance shifts are +0.332 cm^–1 and +2.251 cm^–1 for the upper laser levels pumped by the 10R(36) and the 10R(18) CO₂ laser lines, respectively. Calculated frequencies of the pump and the laser transitions agree with those of the pump CO₂ laser lines and the observed FIR laser lines within estimated accuracy.     

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     

High resolution FTIR spectroscopy of pentafluoroethane: perturbations in the Coriolis doublet of ν4 and ν13

The FTIR spectrum of pentafluoroethane (R125) was measured in the mid infrared region from 900 to 4000 cm⁻¹. Vibrational assignments for R125 are revised by comparison of previous and current experimental data with ab initio calculations at both the MP2/6-311+(d,p) and B3LYP/TZV+(3df,3p) levels of theory. High resolution FTIR spectra were recorded at room temperature and in an enclosive flow cell at a rotational temperature of 140 K. The cold spectrum was sufficiently resolved to enable rovibrational analyses of the overlapping ν₄ (1200.7341 cm⁻¹) and ν₁₃ (1223.3 cm⁻¹) bands, which have a/c hybrid and b-type character, respectively. Ground state combination differences were used to confirm assignment of 2375 lines to ν₄ (J_max = 86, K_{a max} = 50) and 2921 lines to ν₁₃ (J_max = 60, K_{a max} = 54). Effective rotational and centrifugal distortion constants were determined for ν₄, and the polarization ratio was found to be . Severe Coriolis perturbations prevent any satisfactory fit to the ν₁₃ band.     

Tuning characteristics of a high pressure CO2 laser pumped CH3F Raman laser

Conclusion We described a CH₃F Raman laser pumped by a two stage 20 atmospheres CO₂ laser. The emission spectrum of the CH₃F laser at 11 Torr extends from 23 cm^–1 to 45 cm^–1 when the CO₂ laser is scanned over the 9R emission branch at a fixed pump power of 180 mJ. The emission spectrum shows a strong structure with large parts where the FIR energy decreases to zero. This fact makes the use of such a laser for spectroscopic scanning experiments in the FIR difficult. The laser is, however, very suited for working at fixed but adjustable FIR frequencies. The pulse energy in the maxima of the emission characteristics at a pump energy of 180 mJ exceeds 300 J, which corresponds a photon conversion coefficient of more than 6%.     

Far-Infrared Laser Stark Spectroscopy of CH3OD

The high resolution Stark spectra of the singly deuterated methanol isotope, CH₃OD, have been studied using the HCN laser with Stark fields up to approximately 60 000 V/cm. Numerous families of absorption lines have been observed in both parallel and perpendicular polarizations, resulting in the following assignments: with the 311 m line – J _K = 18₁ 18₀ E ₂, _t = 1; and with the 337 m line – J _k = 6₄ 5₃ E ₂, _t = 0 and J _K = 14₆ 13₅ A, _t = 1. Zero-field frequencies for the assigned transitions are in agreement with Fourier transform measurements and those calculated from the available molecular constants.