Far-infrared laser stark spectroscopy of CH3OH and13CH3OH

The high resolution laser Stark spectra of methanol and¹³C-substituted methanol have been studied up to Stark fields of about 60 000V/cm with the HCN and DCN lasers. Numerous families of absorption lines have been observed in both parallel and perpendicular polarizations. For methanol, the transitions J _k =7₅ 6₄ A, _t=0; J _k =11₄ 10₃ E _l , _t=0; and J _k =17₃ 16₂ E₂, _t=0 have been identified while the assignments for¹³C-substituted methanol are J _k =14₈ 15₇ A, _t=0; J _k =15₃ 14₂ A⁺, _t=0; J _k =10₇ 9₆ A, _t=0; and J _k =27₉ 27₈ E₁, _t=0. Zero-field frequencies for the assigned transitions are given with improved accuracy over those calculated from available molecular constants, especially for¹³CH₃OH.     

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.     

Far infrared laser lines and assignments of CH3OH: a review

Methyl alcohol is the most important lasing molecule in the Far-Infrared (FIR) spectral region, and the most widely used for investigation and for applications. Since the last critical review of 1984, over seventy papers have been published dealing with the FIR laser lines and the infrared spectroscopy of CH₃OH. In 1984 we could list about 330 FIR laser lines, 98 of which were measured in frequency and 105 assigned. Since then more than 70 papers were published increasing the number of the known laser lines to 575 (103 measured in frequency). Also the FIR and IR spectroscopy was largely improved thanks to the analysis of high resolution FT spectra, and the number of the correctly assigned laser lines has been increased to 224. The wavenumbers of the assigned lines can now be predicted with an accuracy of about 0.001 cm^–1 or better, thus approaching the accuracy of the experimental frequency measurements.     

Wavelengths for new CH3OH laser lines

Using a grating-tuned CO₂-TEA laser to pump CH₃OH in a metallic-wave-guide resonator, submillimeter laser emissions have been produced by pumping with 36 lines in the 9.4m CO₂ band and with 23 lines in the 10.6m band. Several dozen new SMM laser lines were observed. Wavelengths accurate to within 0.1% are given for 12 previously unmeasured lines between 34m and 225m.     

Operating parameter optimization of optically pumped CH3OH far-infrared laser

By solving the density matrix equations of a quantum system, the output power intensity of an optically pumped CH₃OH FIR laser (CH₃OH-OPFIRL) was calculated by means of iteration method, and the spectral characteristics were got. Base on the calculation, optimization of operating parameters including operating gas pressure, pumped power and output coupling coefficient of the CH₃OH cavity laser were systematically studied. Experimental, a series of FIR emissions of the CH₃OH cavity laser pumped by TEA-CO₂ laser with 9P(16) line were measured. The experimental results were in good agreement with theoretical calculations. The project was supported by the Special Research Foundation of Doctorate Station in University of P.R.C.     

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.     

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.     

A twin optically-pumped far-infrared CH3OH laser for plasma diagnostics

A twin optically-pumped far-infrared CH₃OH laser has been constructed for use in plasma diagnostics. The antisymmetric doublet due to the Raman-type resonant two-photon transition is reproducibly observed at 118.8 m. With the 118.8-m line, it is obtained from the frequency separation of the anti-symmetric doublet that CH₃OH absorption line center is 16±1 MHz higher than the pump 9.7-m P(36) CO₂ laser line center. It is shown that the Raman-type resonant two-photon transition is useful in order to get several-MHz phase modulation for the far-infrared laser interferometer. Some preliminary performances of this twin laser for the modulated interferometer are described.This work was carried out under the collaborating research program at the Institute of Plasma Physics, Nagoya University, Nagoya 464, Japan.     

Frequency measurements of 3 to 11 THz laser lines of CH3OH

We measured the frequencies of 12 far-infrared laser lines generated in a high- frequency Fabry-Perot laser cavity containing methanol, pumped by a CO₂ laser. The frequencies are in the range 2.8 to 11.4 THz (105.4 to 26.2 µm). Ten of the measured frequencies are higher than 7 THz, and help to fill the laser frequency gaps in this region. Five of the measured lines are new. The 11.4 THz line has the highest frequency of an optically pumped laser ever measured with the CO₂ laser heterodyne technique.This work has been financed by the Brazilian Government - Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), and by the United States Government - NASA Grant W-18, 623.Contribution of NIST, not subject to U.S. Copyright.     

On submillimeter laser lines from optically pumped12CH3OH

Several new submillimeter laser lines have been observed in a CH₃OH submillimeter laser, optically pumped by CO₂—laser radiation in a low power pulsed mode.Assignments have been suggested for a number of the lines. A few lines have wavelengths close to atmospheric water vapor absorption peaks, and can be observed only when the air path from the submillimeter resonator exit mirror to the detector is kept short or flushed with dry nitrogen.     

Fourier transform spectroscopy of CH3OH: rotation-torsion-vibration structure for the CH3-rocking and OH-bending modes

High-resolution Fourier transform spectra of CH₃OH have been investigated in the infrared region from 930 to 1450 cm⁻¹ in order to map the torsion-rotation energy manifolds associated with the ν₇ in-plane CH₃ rock, the ν₁₁ out-of-plane CH₃ rock, and the ν₆ OH bend. Upper-state term values have been determined from the assigned spectral subbands, and have been fitted to power-series expansions to obtain substate origins and effective B-values for the three modes. The substate origins have been grouped into related families according to systematic trends observed in the torsion-vibration energy map, but there are substantial differences from the traditional torsional patterns. There appears to be significant torsion-mediated spectral mixing, and a variety of “forbidden” torsional combination subbands with |Δυ_t|>1 have been observed, where υ_t denotes the torsional quantum number (equivalent to υ₁₂). For example, coupling of the (υ₆,υ_t)=(1,0) OH bend to nearby torsionally excited (υ₇,υ_t)=(1,1) CH₃-rock and (υ₈,υ_t)=(1,1) CO-stretch states introduces (υ₆,υ_t)=(1,0)←(0,1) subbands into the spectrum and makes the ν₇+ν₁₂−ν₁₂ torsional hot band stronger than the ν₇ fundamental. The results suggest a picture of strong coupling among the OH-bending, CH₃-rocking, and CO-stretching modes that significantly modifies the traditional energy structure and raises interesting and provocative questions about the torsion-vibration identity of a number of the observed states.     

Theoretical study on the kinetics for OH reactions with CH3OH and C2H5OH

Kinetics and mechanisms for reactions of OH with methanol and ethanol have been investigated at the CCSD(T)/6-311 + G(3df, 2p)//MP2/6-311 + G(3df, 2p) level of theory. The total and individual rate constants, and product branching ratios for the reactions have been computed in the temperature range 200-3000 K with variational transition state theory by including the effects of multiple reflections above the wells of their pre-reaction complexes, quantum-mechanical tunneling and hindered internal rotations. The predicted results can be represented by the expressions k₁ = 4.65 × 10⁻²⁰ × T^2.68 exp(414/T) and k₂ = 9.11 × 10⁻²⁰ × T^2.58 exp(748/T) cm³ molecule⁻¹ s⁻¹ for the CH₃OH and C₂H₅OH reactions, respectively. These results are in reasonable agreements with available experimental data except that of OH + C₂H₅OH in the high temperature range. The former reaction produces 96-89% of the H₂O + CH₂OH products, whereas the latter process produces 98-70% of H₂O + CH₃CHOH and 2-21% of the H₂O + CH₂CH₂OH products in the temperature range computed (200-3000 K).     

Frequency measurements of far infrared12CH3OH laser lines

We have measured the frequencies of 12 known and 3 new submillimeter laser lines obtained by pumping¹²CH₃OH with a cw waveguide CO₂ laser in a Fabry-Perot far infrared resonator. We have also measured the relative polarization and the pumping CO₂ frequency offset for each line.Supported in part by a joint grant with the U.S. National Science Foundation # INT80-19014 and the Brazilian Conselho Nacional de Pesquisas (CNPq).Work of the U.S. Government; not subject to U.S. copyright.     

Methanol laser lines from torsionally excited co stretch states, and from OH-bend, CH3-rock, and CH3-deformation states

Using a quasi-CW CO₂ oscillator-amplifier combination with peak power 300 Watt, we have generated FIR laser emission in weak absorption bands of CH₃OH. 40 new lines are reported, and their wavelengths are measured with a relative accuracy of 5×10^–5. A total of 72 lines are assigned. 34 of these involve torsional n=1, 2, and 3 states of the CO stretch and the vibrational ground state. The remaining lines are associated with the CH₃-rock, OH-bend, and CH₃-deformation modes. The latter are located 1460 cm^–1 above the ground state, and are pumped by simultaneous vibrational excitation and torsional deexcitation.     

The Spectrum of Ground-State Reversed Transition of CH3OH Far-Infrared Laser

Using the CH₃OH molecular energy levels data base management program, we deduced that when a CH₃OH laser pumped by CO₂-9P(16) line, there should be a FIR laser line of 918m wavelength, which corresponding to a transition in ground-state reversed three-level energy system. For the first time, the spectra of ground-state reversed three-level system transitions were calculated by solving the density matrix equations, and the spectrum characteristics of 918m line were studied. Experimentally, the CH₃OH FIR laser line of 918m wavelength was obtained by pumping with a TEA-CO₂ laser. The experimental results were in good agreement with the theoretical calculations.     

Torsion-rotation global analysis and database for the CH3OH isotopomer of methanol

Fourier-transform far-infrared spectra of CH₃¹⁸OH in the 15-470 cm⁻¹ region have been analyzed by means of the Ritz assignment program. The far-infrared data have been combined with the literature microwave and millimeter-wave measurements in a full global fitting of the first three torsional states (ν_t = 0, 1, and 2) of the CH₃¹⁸OH ground vibrational state. The fitted dataset includes 550 microwave and millimeter-wave lines and more than 17 000 Fourier-transform transitions covering the quantum number ranges J ? 30, K ? 15, and ν_t ? 2. With incorporation of 79 adjustable parameters, the global fit achieved convergence with an overall weighted standard deviation of 1.072, essentially to within the assigned measurement uncertainties of ±50 kHz for almost all of the microwave and millimeter-wave lines and ±6 MHz (0.0002 cm⁻¹) to ±15 MHz (0.0005 cm⁻¹) for the Fourier-transform far-infrared measurements. Based on the global fit results, a database has been compiled containing transition frequencies, quantum numbers, lower state energies and transition strengths. This database will provide support for present and future astronomical studies, such as the on-going Orion surveys in preparation for the launch of the Herschel Space Observatory, in identifying isotopic methanol contributions to interstellar spectra.     

Measurements and assignments of new large offset CD3OH FIR laser lines

By using an acoustooptic modulator we extend the 300 MHz tunability of a waveguide CO₂ laser to 480 MHz. The CD₃OH was optically pumped by the 10R(32), 10R(34), and 10R(36) CO₂ laser lines, and 17 new FIR laser lines were discovered. The Stark effect on previously known FIR laser lines was investigated, and some tentative FIR laser lines assignments are suggested.     

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.     

New CH2F2 FIR laser lines pumped by a tunable WG CO2 laser

8 new large offset FIR laser lines of CH₂F₂ have been discovered by pumping with a high tunability waveguide CW CO₂ laser. Optoacoustic measurements of CH₂F₂ have also been performed and the pump offsets of the new and of previously known lines have been measured and checked. Some assignments are proposed and a few assignments found in literature are checked     

FIR gain measurements in cw laser pumped CH3OD

Direct measurements of small signal and saturated gain in cw laser pumped CH₃OD are reported for three lasing transitions of 57 m, 82 m and 103 m. The 57 m transition has a measured gain of 0.6/m, the strongest gain in methanol reported so far. Moreover small gain saturation of this line makes it to be one of the strongest known cw FIR laser lines.