Fourier spectrum of CH3OH between 950 and 1100 cm−1

The infrared spectrum ofCH₃OH between 950 and HOOcm⁻¹ has been measured by a high resolution Fourier transform spectrometer. This spectral region is of particular interest because of its overlapping with the CO₂ laser emissions used for exciting the CH₃OH laser. A catalog of 3410 assigned lines is presented, as well as the Taylor development tables for evaluating the energies of the upper levels of the corresponding transitions.     

Confirmation of far infrared laser assignments from CH3-deformation and CH3-rocking states of optically pumped methanol

High-resolution Fourier transform spectroscopy has been applied to confirm previously proposed assignments for nine far infrared (FIR) laser lines from the CH₃-deformation state of CH₃OH and one line from the CH₃-rocking state. Accurate frequencies are deduced for the observed and other predicted FIR laser transitions. FIR torsional branch frequencies in the ground state which were used in the confirmation are presented. Comments are also made on the OH-bending mode of CH₃OH.     

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.     

Torsional refilling transitions in tea-pumped CH3OH fir lasers with associated high-resolution fir spectra

It is proposed that a number of the high-frequency far-infrared (FIR) laser lines observed when CH₃OH is optically pumped by high-power CO₂ TEA lasers can be identified as refilling torsional transitions within the vibrational ground state. Assignments are presented for 8 such TEA-pump/FIR-laser refilling systems. To provide support for the assigned laser frequencies, high-resolution Fourier transform FIR spectra of CH₃OH have been obtained and partially analyzed in the torsional transition region.     

One watt,far infrared CH3OH laser

Peak powers near 1 watt have been observed on the CH₃OH laser line at 570.5 μm as well as on each of three new CH₃OH laser lines produced by pumping a far infrared guided wave cavity with a 0.5 MW helical CO₂-TEA laser. The new lines have wavelengths of 58.1, 65.1 and 451.9 μm. For all four lines the optimum CH₃OH pressure was between 2.3 and 3 torr, and laser action at 65.1 μm persisted up to a pressure in excess of 9 torr.     

IR absorption measurements and new FIR emission lines in CH3OH by use of a frequency-tunable CW waveguide CO2 laser

The IR absorption in CH₃OH in the vicinity of CO₂ laser lines has been measured quantitatively by use of a 300 MHz tunable waveguide CO₂ laser with output powers of about 3 W. Information on frequency offsets from the CO₂ line centers, small signal and saturated absorption coefficients of FIR laser pump transitions is obtained. Some stronger pump transitions with frequency offsets larger than 50 MHz gave rise to the observation of 8 new FIR emission lines with wavelengths from 43 to 125 μm.     

12CH3OH and 13CH3OH optically pumped by the 10P and 10HP bands of a pulsed CO2 laser: New far-infrared laser emissions and assignments

We have re-investigated the ¹²CH₃OH and the ¹³CH₃OH molecules as optically pumped far-infrared laser sources. We have used our new waveguide pulsed-high-peak-power CO₂ laser for pumping, finding 20 new far-infrared laser lines emitted by ¹²CH₃OH and seven emitted by ¹³CH₃OH. For each line we report wavelength, pump offset from the center of the exciting CO₂ line, relative polarization, optimum operating pressure and intensity. The LaseRitz program was able to assign one of the new laser systems of ¹²CH₃OH, involving two new far-infrared laser lines.PACS 42.55.Lt; 42.62.Fi     

Line profile study by diode laser spectroscopy in the CH4ν2 + ν4 band

We present a complete study on four methane lines for two atmospheric micro-windows (in the ν₂ + ν₄ absorption band) used for the determination of atmospheric methane concentrations with ground-based Fourier transform spectrometers. Thanks to our tunable diode laser (TDL) spectrometer with active wavenumber control and step-by-step recording mode we have improved the accuracy on intensity, broadening, narrowing, and pressure shift parameters. To make our results directly useable in atmospheric models which usually assume a Voigt line shape, we have parameterised an effective-broadening parameter γ_Voigt (P) for each line and each gas mixture (CH₄-N₂ and CH₄-O₂). When this parameterisation is used to fit a “true” line profile, the same concentration as with more sophisticated models is retrieved using a consistent set of spectroscopic parameters in both approaches.     

Spectroscopy of the excited C-O stretching Q branch of 13CD3OH: Measurement and assignment of new FIR laser lines

The Q branch of the C-O stretching fundamental band of ¹³CD₃OH has been investigated. Starting from a high resolution (4 × 10⁻³cm⁻¹) infrared Fourier transform spectrum and using a waveguide CO₂ laser of 300 MHz tunability and an acoustooptic modulator for an extension of ±90 MHz, 31 new FIR laser lines have been observed. The related absorptions have been measured by means of optoacoustic detection. The frequency of one new FIR laser line was also measured. Eight tentative assignments are proposed for the IR absorption and FIR laser emissions.     

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.     

Narrowing and Broadening Parameters for H2O Lines in the ν2 Band Perturbed by Nitrogen from Fourier Transform and Tunable Diode Laser Spectroscopy

Collision effects on water vapor line profiles perturbed by nitrogen at room temperature have been studied by Fourier transform and tunable diode laser spectroscopy. Narrowing effect due to molecular confinement (Dicke effect) has been observed for P and Q branch lines of the ν₂ band of H₂O with Fourier transform spectrometer. Narrowing and broadening parameters have been determined using the soft and hard collision models. A more precise study on three R-branch lines with a frequency stabilized diode laser spectrometer allows to perform the comparison between the two collision models at low pressure and to analyze the different narrowing effects when the pressure increases taking into account the molecular confinement and the absorber speed dependent effects.     

High resolution spectrum of Ch3OH between 8 and 100cm−1

The FIR spectrum of CH₃OH between 8–100 cm⁻¹ has been measured by a high resolution Fourier transform spectrometer. A computer best fit program, based on the Taylor series expansion of the energy levels, has been used for the line assignments. The region between 40–100 cm⁻¹ is presented for the first time. The region between 8–40 cm⁻¹, covered in a previous work, is revisited in the light of the new measurements at higher frequencies, and new assignments are given. The available microwave and radio-frequency assignments have been inserted into the fit program. A catalogue of 6725 assigned MW and FIR lines below 101.8 cm⁻¹ is presented.     

Far infrared laser lines produced by methanol and its isotopic species: A review

Methanol (CH₃OH) is considered today one of the most important active media for the generation of laser radiation in the far-infrared (FIR) spectral region. Together with ten of its other isotopic species, it is responsible for the major part of the laser lines generated by the optical pumping technique. Due to the extreme importance of those molecules as laser generators, we understood that there was a necessity of a comprehensive work which would include as much pratical information as possible about each line.Chang et al⁽¹⁾ early recognized methanol as a source of strong FIR laser lines. Since then, more than 100 papers were published containing information about new laser emission. Recently, Moruzzi et al⁽¹¹⁴⁾ presented a review of 575 lines produced by¹²CH₃OH. In the present paper, we have extended the review to the various isotopic modifications of this molecule (namely¹³CH₃OH, CD₃OH,¹³CD₃OH, CD₃OD,¹³CD₃OD, CH₃OD, CH ₃ ¹⁸ OH, CH₂DOH, CH₂DOD and CHD₂OH), a total of nearly 2000 lines with wavelengths ranging from 19µm to 3030µm.     

Experimental study on miniature pulsed CH3OH far-infrared laser

Using a grating tuned TEA-CO₂ laser with 9P(16) line to pump a 10cm or 20cm long miniature Fabry-Perot cavity CH₃OH laser, pulsed far infrared(FIR) lines of 570.6um and 918um wavelengths were observed, the latter is a new line. Operation performance and spectral characteristics of the miniature CH₃OH laser were studied. The project was supported by the Special Research Foundation of Doctorate Station in University of P.R.C.     

CH<Subscript>3</Subscript>OH optically pumped by a <Superscript>13</Superscript>CO<Subscript>2</Subscript> laser: new laser lines and assignments

We report 12 new THz (far-infrared) laser lines from methanol (CH₃OH), ranging from 58.1 μm (5.2 THz) to 624.6 μm (0.5 THz). A ¹³CO₂ laser of wide tunability (110 MHz) has been used for optical pumping, allowing access to previously unexplored spectral regions. Optoacoustic absorption spectra were used as a guide to search for new THz laser lines, which have been characterized in wavelength, polarization, offset, relative intensity, and optimum operation pressure. For 20 laser lines previously observed, we have measured the absorption offset with respect to the ¹³CO₂ laser line center. PACS 33.20.Ea; 33.20.Vq; 33.80.-b     

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     

The kinetics of the gas-phase reaction between methanol and boron trichloride

Using a spectroscopic complex designed for studying the kinetics of chemical reactions, the rate constant for the gas-phase reaction between a Lewis base and a Lewis acid—CH₃OH + BCl₃ → CH₃OBCl₂ + HCl—at at room temperature and pressures of 1.5–27.9 Torr has been derived for the first time. The complex comprises a reactor embedded in the optical system of a commercial AF-3 Fourier transform IR spectrometer capable of recording the spectra of reactants during the process. The reaction mechanism has been analyzed.     

Determination of dipole moments in vibrationally excited CH3OH by combined far infrared laser Stark effect and transferred Lamb dip spectroscopy

Optically pumped fir laser lines in CH₃OH are studied by combined fir emission Stark effect and transferred Lamb dip spectroscopy. Effective dipole moments are determined, which are interpreted as being associated with hybridization of CO stretch states and states of a different vibrational mode, with same J but different K. Far-infrared laser lines originating from large offset absorption lines, which are Stark-tuned into coincidence, are assigned. The results suggest that the mode interacting with the CO stretch is the CH₃ symmetric rocking mode.     

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.     

Measurement and assignment of new FIR laser lines in12CH3OH and13CH3OH

We have found twelve new FIR laser lines in¹²CH₃OH and thirty three in¹³CH₃OH. Both molecules were pumped by a regular cw CO₂ laser. We have also assigned 20¹³CH₃OH laser lines to specific rotational energy levels in the excited C-O stretchhindered rotation combined states