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     

Frequency and efficiency measurements on FIR laser lines close to the N+ 3 P 2−3 P 1 transition

FIR laser lines close to the N^{+ 3} P ₂–³ P ₁ transition at 122 m can be used as a local oscillator for heterodyne detectors. The frequencies of some candidate laser lines from CH₂F₂,¹³CH₃OH, CD₃OD, and CD₃OH have been measured and the output power of the most interesting lines has been optimized.     

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.     

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.     

IR and FIR spectroscopy of 13CD3OH around the 10P(22) and 10P(24) CO2 laser lines: New FIR laser emissions,frequency measurements and assignments

By using high resolution infrared Fourier transform data on ¹³CD₃OH and the 10P(22) and 10P(24) lines of a waveguide CO₂ laser to optically pump this methanol isotope, eight new FIR laser lines were observed. The frequencies of five laser lines were directly measured by heterodyne detection with already known laser lines. Particularly interesting are the lines pumped by the 10P(24) line, since a triade of emissions could be completely assigned.     

Optically Pumped Far-Infrared Laser Lines of Methanol Isotopomers: 12CD3OH, 12CH3OD, and 12CH2DOH

Twenty-seven new FIR, far-infrared, laser lines from the isotopomers of methanol: ¹²CD₃OH, ¹²CH₃OD, and ¹²CH₂DOH, were obtained by optically pumping the molecules with an efficient cw CO₂ laser. The CO₂ laser provided pumping from regular, sequence, and hot-band CO₂ laser transitions. The 2 m long far-infrared cavity was a metal-dielectric waveguide closed by two, flat end mirrors. Several short-wavelength (below 100 m) lines were observed. The frequencies of 28 laser lines observed in this cavity (including new lines and already known lines) were measured with a fractional uncertainty limited by the fractional resetability of the far-infrared laser cavity, of 2 parts in 10⁷.     

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.     

FIR Laser Lines from CH3OD: A Review

The methanol isotopic species CH₃OD has also proved to be an efficient and powerful medium to generate radiation in the far infrared (FIR) region. After the critical review of 1994, six papers have been published dealing with new FIR laser lines from this molecule. As a consequence of the use of wide tunability waveguide CO₂ lasers as well as a new pulsed CO₂ laser operating at hot and sequential bands, as of optical pumping sources, the total number of the FIR laser lines increased from 122 in 1994 to 227 today. In this communication we present an updated and complete catalogue of FIR laser lines generated from CH₃OD. Information on wavelength, offset, relative polarization, intensity, and optimum operation pressure is generally available.     

Infrared Optoacoustic Spectroscopy of 13CD3OD Around 9P CO2 Laser Lines

In this work we present the results of an investigation about Doppler limited infrared absorbing transitions of the in-plane methyl-rocking and the asymmetric methyl deformation modes of ¹³CD₃OD by means of optoacoustic detection. This is an alternative and attractive technique to be applied to this methanol isotopomer, in comparison to Fourier transform spectroscopy. In fact the contamination problem associated with the fast exchange of OD by OH in the molecule limits the use of the Fourier transform technique. Using a waveguide CO₂ laser of 290 MHz tunability on each line we were able to observe 20 IR absorptions, most of them of large offset. The data will be useful in theoretical analysis of this molecule, as well as in the generation of FIR laser radiation in optically pumped molecular laser.     

Discovery and frequency measurement of short-wavelength far-infrared laser emissions from optically pumped <Superscript>13</Superscript>CD<Subscript>3</Subscript>OH and CHD<Subscript>2</Subscript>OH

A three-laser heterodyne system was used to measure the frequencies of twelve previously observed far-infrared laser emissions from the partially deuterated methanol isotopologues ¹³CD₃OH and CHD₂OH. Two laser emissions, a 53.773 μm line from ¹³CD₃OH and a 74.939 μm line from CHD₂OH, have also been discovered and frequency measured. The CO₂ pump laser offset frequency was measured with respect to its center frequency for twenty-four FIR laser emissions from CH₃OH, ¹³CD₃OH and CHD₂OH. PACS 07.57.Hm; 42.55.Lt; 42.62.Eh     

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.     

The a-Type K = 0 Microwave Spectrum of the Methanol Dimer

The rotational spectrum of (CH₃OH)₂ has been observed in the region 4-22 GHz with pulsed-beam Fabry-Perot cavity Fourier-transform microwave spectrometers at NIST and at the University of Kiel. Each a-type R(J), K_a = 0 transition is split into 15 states by tunneling motions for (CH₃OH)₂, (¹³CH₃OH)₂, (CH₃OD)₂, (CD₃OH)₂, and (CD₃OH)₂. The preliminary analysis of the methyl internal rotation presented here was guided by the previously developed multidimensional tunneling theory which predicts 16 tunneling components for each R(J) transition from 25 distinct tunneling motions. Several isotopically mixed dimers of methanol have also been measured, namely ¹³CH₃OH, CH₃OD, CD₃OH, and CD₃OD bound to ¹²CH₃OH. Since the hydrogen bond interchange motion (which converts a donor into an acceptor) would produce a new and less favorable conformation from an energy viewpoint, it does not occur and only 10 tunneling components are observed for these mixed dimers. The structure of the complex is similar to that of water dimer with a hydrogen bond distance of 2.035 Å and a tilt of the acceptor methanol of 84° from the O-H-O axis. The effective barrier to internal rotation for the donor methyl group of (CH₃OH)₂ is ν₃ = 183.0 cm⁻¹ and is one-half of the value for the methanol monomer (370 cm⁻¹), while the barrier to internal rotation of the acceptor methyl group is 120 cm⁻¹.     

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.     

New submillimetre laser lines from CH3OD and CD3OD

Thirteen new submillimetre emission lines have been observed when pumping CH₃OD using isotopic CO₂ lasers, and fourteen when pumping CD₃OD. Three isotopic CO₂ lasers were used¹²C¹⁶O₂,¹²C¹⁸O₂, and¹³C¹⁶O₂. The new lines were observed in a Fabry-Perot resonator. The wavelength ranges observed were from 55 to 320 m for CH₃OD and from 66 to 531 m for CD₃OD. The polarisation of the submillimetre laser lines relative to the CO₂ pump line has also been determined.     

13CD3OH and12CD3OH optically pumped by a13CO2 laser: Observations and assignments of FIR laser lines

In this work we report the first observation of FIR laser lines from¹³CD₃OH pumped by the¹³CO₂ isotope laser. Using the same pump we have also found 3 new lines from¹²CD₃OH. Tentative assignments for the absorption and emission transitions of the observed lines are also proposed.Work supported by FAPESP. CNPq, FAEP/UNICAMP-Brasil and NSF-USA     

Reinvestigation of far-infrared laser emissions from hydrazine and deuterated isotopes of difluoromethane and methanol

Hydrazine (N₂H₄) and the deuterated isotopes of difluoromethane (CD₂F₂) and methanol (CH₃OD and CD₃OH) have been reinvestigated as sources of far-infrared (FIR) laser emissions using an optically pumped molecular laser system designed for wavelengths below 150 microns. With this system, seven FIR laser emissions from optically pumped N₂H₄, CH₃OD and CD₃OH were discovered with wavelengths ranging from 54.0 to 185.0 m. In addition, the polarizations of eight previously observed laser emissions from optically pumped N₂H₄, CH₃OD and CD₂F₂ were measured for the first time. All laser emissions are reported with their operating pressures, relative polarizations and wavelengths, measured to ±0.5 m. The effectiveness of this particular system in generating short-wavelength laser emissions has been further demonstrated by the improvement in output power observed from nine known FIR laser emissions. PACS 07.57.Hm; 42.55.Lt     

Laser Lines and Frequency Measurements of Fully Deuterated Isotopomers of Methanol

Fully deuterated isotopomers of methanol (¹²CD₃OD and ¹³CD₃OD) were optically pumped with a CO₂ laser. Five new far-infrared laser lines were discovered in ¹²CD₃OD and 25 in ¹³CD₃OD in the range 43.697 to 719.426 m. The frequencies of these new and some previously reported laser lines, the pump offset, the relative polarization, the relative intensity, and the optimum pressure of operation were measured.     

New FIR laser lines and frequency measurements in CD3OD

Twenty-four new submillimeter laser lines in fully deuterated methyl alcohol (CD₃OD) in the wavelength range from 52 to 328 m have been obtained in a Fabry-Perot FIR resonator by optically pumping the methanol with a cw CO₂ laser. We have made accurate wavelength measurements and have determined the relative polarization of most of the known CD₃OD laser lines. The frequencies of 13 of the strongest lines were also measured.Contribution of the U.S. Government, not subject to copyright.     

Pure Rotational Raman Spectra of Vapor Phase Methanols

Abstract

The rotational Raman spectra of four vapor phase isotopic methanols, CH₃OH, CH₃OD, CD₃OH and CD₃OD, have been reported for the first time in the wavenumber regions from 5 to 100–120 cm^?1. The major parts of the spectra consist of bands equispaced at 3.19, 3.04, 2.56 and 2.46 cm^?1 intervals, respectively, and have been interpreted as the pure rotational S-branch transitions.