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.     

New fir laser lines and frequency measurements from optically pumped13CD3OH3

We report the discovery of 57 new fir laser lines from¹³CD₃OH molecule optically pumped by a waveguide CO₂ laser of 300 MHz tunability. For all lines, precise frequency offset measurements between the CO₂ line center and the center of the absorbing¹³CD₃OH line were performed using the transferred Lamb-Dip technique. We have also measured directly the frequency of seven FIR laser lines by heterodyning with already known laser lines. We present a complete list of all known laser lines (134) and frequency measurements (24) for this molecule.Work supported by CNPq, FAPESP, FAEP-Brasil, and CNR-Italia     

Optically pumped 13CD3I: new TeraHertz laser transitions

We investigated the ¹³CD₃I isotopomer of methyl iodide as a source of TeraHertz laser radiation using the optical pumping technique. We used a pulsed waveguide CO₂ laser as the pump laser and an open Fabry–Pérot cavity for new laser line generation. We discovered 18 new laser lines with wavelengths ranging from 308.4 to 1132.7 μm, plus two lines previously assigned to ¹²CD₃I. All of the lines were characterized in wavelength, pump frequency offset, optimum pressure of operation, and relative polarization and intensity.     

FIR laser assignments and frequency predictions for optically pumped13CD3OH by high-resolution Fourier transform spectroscopy

Continued study of the high-resolution Fourier transform spectroscopy (FTS) of the fundamental CO-stretching band of¹³CD₃OH has given additional insight into the far-infrared (FIR) laser emission observed when this molecule is optically pumped by a CO₂ laser. Eleven IR-pump/FIR-laser transition systems are considered. Seven represent completely new assignments, while four have been presented previously but are discussed further with reference to recently reported experimental data. Ten of the assignment schemes have been rigorously checked by forming closed combination loops, and accurate FIR laser wavenumbers have been obtained. The superiority in precision of the FIR laser wavenumbers determined from FTS combination loops over those from traditional wavelength measurements is demonstrated.     

Experimental investigation of13CD3OH infrared transitions by means of optoacoustic spectroscopy

A systematic investigation of¹³CD₃OH infrared transitions around CO₂ laser line emissions is performed by means of optoacoustic detection. Using a waveguide CO₂ laser of 290 MHz tunability and, in some cases, an acoustooptic modulator to provide an extension of 180 MHz, 108 transitions are observed. Measurements of pump off-set and relative intensity have been performed. The data may be compared with those previously reported of high resolution Fourier Transform spectroscopy.Work supported by: FAPESP, CNPq, FAEP — Brasil CNR — ItaliaPermanent address: Depto de Ciências, FEIS-UNESP (15378) I.Solteira-SP, Brasil     

Infrared optoacoustic spectroscopy of13CD3OD around the 10R and 10P CO2 laser lines

In this work we present the results of an investigation about Doppler limited infrared absorbing transitions of the C-O stretching vibrational mode of¹³CD₃OD by means of optoacoustic detection. This technique is an alternative, more sensitive and of higher resolution than the Fourier transform spectroscopy which is applied to this methanol isotopomer, due to the contamination problem associated with the fast exchange of OD by OH in the molecule. Using a waveguide CO₂ laser of 290 MHz tunability on each line we were able to observe 69 absorptions, most of then of large offset. The data will be useful in theoretical analysis of this sample, as well as a guide in the search for new FIR laser lines.     

New far infrared laser lines obtained by optically pumping13CD3OD

We have obtained laser action on 34 far infrared lines for the first time in fully deuterated methyl alcohol with the¹³C isotope (¹³CD₃OD), and we have measured the frequency of 13 lines. The molecule was pumped by a cw CO₂ laser. We have measured the wavelength, the relative polarization, the relative intensity of most lines, the frequency, and the CO₂ pump frequency offset of the strongest lines. The new lines are distributed in the wavelength region from 75.27 m to 464.7 m.Supported in part by a joint grant with the U.S. National Science Foundation grant # INT 80-19014 and the Brazilian Conselho Nacional de Pesquisas (CNPq).     

New optically pumped FIR laser lines in CD3OH

In this work we report laser action in 69 new FIR laser lines in CD₃OH optically pumped by a regular cw CO₂ laser. We have performed measurements of laser wavelength, optimum pressure of the gas, relative polarization and intensity on all lines, including some previously known.     

Vibrational and Rotational Spectroscopy of 13CD3OD

We have used Fourier Transform spectral data on the C-O stretching mode of ¹³CD₃OD in order to perform a vibro-rotational analysis for this molecule. We have estimated a few molecular parameters of the ground and C-O stretching vibrational modes. Based on these parameters, and by using the Kwan-Dennison model, we propose assignments for a number of far-infrared laser transitions of ¹³CD₃OD.     

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.     

Electric field effects on roto-vibrational transitions of13CD3OH1

We used a Stark-Optoacoustic cell and hybrid waveguide resonators to perform an Infrared and Far Infrared Stark Spectroscopy study on some transitions of¹³CD₃OH. Different behaviours of the transitions in the presence of a d.c. electric field were observed. The Stark splittings of six FIR laser lines ranging from 34 to 136 MHz/kVcm^–1 were determined. The analysis of the behaviour of the IR and FIR transitions in the presence of the external electric fields gives important and exclusive information on the levels involved in the transitions.Work Supported by FAPESP, CNPq, FAEP - Brazil, and CNR - Italy.     

New FIR laser lines and frequency measurements for optically pumped CD3OH

Twenty new cw FIR laser lines in CD₃OH, optically pumped by a CO₂ laser, are reported. The frequencies of 39 of the stronger laser lines were measured relative to stabilized CO₂ lasers with a fractional uncertainty, as determined by the reproducibility of the FIR frequency itself, of 2 parts in 10⁷.Contribution of the U.S. Government, not subject to copyright.     

Heterodyne frequency measurements of COF2, CD3F,13CD3F, and C2H5I lasers

Heterodyne frequency measurements are reported for twenty optically pumped laser lines from various molecules including COF₂, CD₃F,¹³CD₃F, and C₂H₅I.     

Diode laser and Fourier transform spectroscopy of the13CH3OH C-O stretching mode

In this work we present high resolution Doppler limited absorption spectra measurements of the C-O stretching mode of¹³CH₃OH, obtained from diode laser spectroscopy, and the Fourier Transform spectrum obtained at 0.12 cm^–1 resolution. By using these data and previously known spectroscopic information, we determined the frequency and the J quantum number for the multiplets of the P and R(J) branches of the C-O stretching fundamental band. Infrared transitions in coincidence with emission lines of the regular CO₂ laser and some of its isotope parents are pointed out.     

High power pulsed fir laser lines from CD3OH

Sixteen FIR laser lines have been observed by optical pumping of CD₃OH with a tunable single-mode TEA CO₂ laser. Particularly large outputs are observed at 70.6 μm (10 P20 pump), 69.9 μm (10 R22), 42.3 μm (10 R6), and 105.3 μm and 41.7 μm (10 R8).     

Applications of high resolution spectroscopy to the identification of far-infrared laser emission from optically pumped13CH3OH

High-resolution infrared (IR) and far infrared (FIR) Fourier transform absorption spectra have been employed to investigate assignments of FIR laser lines reported from optically-pumped¹³CH₃OH. The spectroscopic measurements are used in conjunction with the reported IR pump and FIR laser frequencies to form closed combination loops for several systems, serving to confirm the assignments and in some cases to improve the accuracy of the FIR laser frequencies. Frequency predictions from combination differences are also presented for a number of potential new FIR laser lines.     

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.     

New FIR laser lines from an optically pumped far-infrared laser with isotopic 13C16O2 pumping

A ¹³C¹⁶O₂ laser optically pumping a FIR laser has resulted in 17 new FIR cw emissions from 78.5 μm to 917 μm. The FIR media were: CD₃OD, CH₃OD, CD₃OH, NH₃ and ¹⁵NH₃. Interesting effects have been observed with a combination of NH₃ and CD₃OD resulting in a new FIR emission. Two new FIR emissions at 181.5 μm and 355.5 μm have been observed with a ¹²C¹⁶O₂ laser optically pumping CD₃OD.     

Infrared and far-infrared spectroscopy of CH3OH: TeraHertz laser lines and assignments

We use a ¹³CO₂ laser as optical pumping source to search for new THz laser lines generated from ¹³CH₃OH. Nineteen new THz laser lines (also identified as far-infrared, FIR) ranging from 42.3 μm (7.1 THz) to 717.7 μm (0.42 THz) are reported. They are characterized in wavelength, offset, relative polarization, relative intensity, and optimum working pressure. We have assigned eight laser lines to specific rotational energy levels in the excited state associated with the C-O stretching mode.     

A review of optically pumped far-infrared laser lines from methanol isotopes

The technique of optical pumping in polar molecules is the most efficient for Far-Infrared (FIR) laser generation, providing also a versatile and powerful tool for molecular spectroscopy in this spectral region. Methanol (CH₃OH) and its isotopic varieties are the best media for optically pumped FIR laser, with over thousand lines observed, and the most widely used for investigations and applications. In this sense, it is important organize and make available catalogues of FIR laser lines as complete as possible. Since the last critical reviews of 1984 [1] on methanol and its isotopic varieties [2,3,4], over hundred papers have been published dealing with hundreds of new FIR laser lines. In 1992 a review of FIR laser lines from CH₃OH was presented [5]. In this communication we extend this work to the other methanol isotopes, namely CH₃OD, CD₃OH, CD₃OD,¹³CH₃OH,¹³CD₃OH,¹³CD₃OD, CH₃ ¹⁸OH, CH₂DOH, CHD₂OH and CH₂DOD.Work supported by FAPESP, CNPq, FAEP-Brasil, and CNR-Italia