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     

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.     

Frequencies of cw FIR laser lines from optically pumped CH2F2

The frequencies of 48 optically pumped cw FIR CH₂F₂ laser lines have been measured relative to stabilized CO₂ lasers. Uncertainties are estimated to be about 5 parts in 10⁷.     

Optically pumped submillimeter laser lines from CH2F2 and CD2Cl2 using a12C18O2 CW laser

Thirty-nine new submillimetre laser lines in CH₂F₂ and twelve in CD₂Cl₂ have been obtained in a Fabry-Perot FIR resonator by optically pumping with a CW¹²C¹⁸O₂ laser. The wavelength range obtained for CH₂F₂ is 126m to 1091m and for CD₂Cl₂ 212m to 774m. The wavelength measurements are accurate to within 5.10^–3. The relative polarisations of the pump laser and the FIR laser output were also determined. Tentative assignments of the IR and FIR transitions were made using existing microwave data.     

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.     

Frequency measurements on far-infrared emissions from12C16O2-pumped methyl chloride and from12C18O2-pumped difluoromethane

The frequencies of 42 far-infrared laser lines have been measured by mixing with high-order harmonics of microwave frequencies in a Josephson junction. A total of 5 emissions between 334 and 1887 m have been measured from¹²C¹⁶O₂-pumped methyl chloride (CH₃Cl) and 37 emissions between 116 and 1092 m in¹²C¹⁸O₂-pumped difluoromethane (CH₂F₂). Additional data is given on the laser emission characteristics.Division of Electrical Science, National Physical Laboratory     

IR and FIR Spectroscopy of 13CH3I

We have investigated the ¹³CH₃I isotopomer of methyl iodide as a source of Far Infrared (FIR) laser radiation using the optical pumping technique. The molecule is pumped by using a pulsed waveguided CO₂ laser, driven by a novel all solid state power supply that lases on the 10HP band as well as the regular bands. We discovered and assigned two new FIR laser emissions and we give further spectroscopic information about polarization and pump frequency offset for five already known lines.     

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.     

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.     

Optically pumped CW fir laser: New submillimeter laser emissions from CH2DOH, CH3I, CD3I, and trioxymethylene

We obtained twelve new far infrared laser transitions by optically pumping the CH₂DOH, CH₃I, CD₃I and Trioxymethylene molecules with a CW CO₂ laser having a tunability range of 280 MHz. We measured the wavelength, polarization, relative intensity and pump offset relative to the CO₂ center frequency for all the new lines.     

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.     

New FIR laser lines from optically pumped C2H3F, C2H3Cl, C2H3Br, C2H3CN, C2H5F, CH2CF2, HCOOH and CH3Br

Twenty-seven new cw far infrared laser lines with wavelengths between 137 and 988m have been observed from optically pumping C₂H₃F, C₂H₃Cl, C₂H₃Br, C₂H₅F, C₂H₃CN, CH₂CF₂, HCOOH and CH₃Br with a CO₂ laser. The wavelengths of these FIR laser lines were determined together with their optimum pressures and relative intensities.     

Laser stark spectroscopy of13CH3F

The far-infrared laser Stark spectrum of¹³CH₃F has been observed using the 190 m line of the DCN laser. The spectrum was taken at room temperature for both parallel and perpendicular polarizations up to 60,000V/cm. We identify the transition as J_k=32₁₄31₁₄ in the ground vibrational state. The measured zero-field frequency for this transition is in agreement with that calculated from the available molecular constants.     

A Theoretical Study of ãA2 CH2

The potential energy surface and dipole moment surfaces of the ã⁴A₂ electronic state of CH₂⁺ are calculated ab initio using an augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set, with the incorporation of dynamical correlation using the coupled cluster method with single and double excitations and perturbatively connected triple excitations [CCSD(T)]. We use these surfaces in the MORBID program system to calculate rotation and rotation-vibration term values for ã-state CH₂⁺, CD⁺₂, and CHD⁺ and to simulate the rotation and rotation-vibration absorption spectrum of CH₂⁺ in the ã⁴A₂ electronic state. Our work is motivated by studies of CH₂⁺ that use the Coulomb explosion imaging technique and by the goal of predicting spectra that may be obtained from discharge sources. Although the ã state is the lowest-lying excited state above the X?/Ã ground state pair, it turns out to be relatively high-lying, and we determine that T_e(ã)=30447.5 cm⁻¹. The equilibrium bond angle for ã-state CH₂⁺ is only 77.1°; as a result the asymmetric top κ value is close to 0, and the molecule is equally far from the oblate and prolate symmetric top limits in this electronic state.     

Frequencies and wavelengths from a new, efficient FIR lasing gas: CD2F2

We report for the first time wavelength, relative polarization, and frequency measurements for 47 new cw FIR laser lines in the wavelength region from 120 to 1714 m, all obtained by optically pumping CD₂F₂ with a CO₂ laser. Relative output powers were also measured. For comparison, the 189.8 m line pumped by R_I(34) is nearly five times as efficient as the 118.8 m methyl alcohol line.Contribution of the U.S. Government, not subject to copyright.     

Optically-Pumped Far-Infrared Laser Lines of Methanol Isotopomers: 12CH3OH, 12CH3OD, and 12CH2DOH

Twenty-seven new 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.     

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.     

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 Matrix Isolation Spectrum of the CH2 Ion

For CH₂⁺ molecular ions at 5 K we simulate the infrared absorption spectrum, and tabulate all strong absorption lines from 0 to 16 000 cm⁻¹. We use ab initio potential energy, dipole moment, and transition moment surfaces in conjunction with our program system RENNER, which allows for the Renner-Teller effect and spin-orbit coupling in a full-dimensions calculation. This is done for the purpose of guiding our search for the matrix isolation spectrum; our attempts at finding this spectrum are also described.     

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.