Multiple submillimeter emissions of difluoromethane pumped by cw 9R(6) laser line of 12C16O2

Pumped by the 9R(6) ¹²C¹⁶O₂ laser lines, CH₂F₂ produces five SMM emissions. Levels involved in this process are identified with the help of a Fourier transform spectrum. Among these emissions we find cascade and intervibrational transitions allowed by Coriolis resonance between v₉ and v₃.     

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     

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.     

Absorption and line-broadening of 12C18O2 at 2.7 μm

Pressure broadening coefficients have been measured for ¹²C¹⁸O₂ at 2.7 μm broadened by buffer gas species CO₂, H₂, He, O₂, N₂, Ar, and Xe. The results, expressed as self-broadening efficiencies, are compared with data for other transitions from 1.6 to 10.4 μm.     

Determination of laser line frequencies and vibrational-rotational constants of the 12C18O2, 13C16O2, and 13C18O2 isotopes from measurements of CW beat frequencies with fast HgCdTe photodiodes and microwave frequency counters

The frequencies of ¹²C¹⁸O₂, ¹³C¹⁶O₂, and ¹³C¹⁸O₂ isotope lasers have been measured to better than 3 MHz (0.0001 cm^?1) by comparing with a ¹²C¹⁶O₂ reference laser. Heterodyne techniques were used to generate 139 difference frequencies in a liquid nitrogen cooled HgCdTe photodiode. Microwave frequency counter measurements of the difference frequencies were then used to calculate new values for the band centers and rotational constants of the rare isotopes. Procedures to achieve further improvements are discussed.     

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.     

Spectrum of 13C16O2 at 2.8 μm

A theoretical model for the rovibrational analysis of clustered vibrational states for tetrahedral molecules is presented. The results of a comprehensive study of the five bands ν₁, ν₃, 2ν₂, ν₂ + ν₄, and 2ν₄ of ¹²CH₄ are reported. The Hamiltonian has been developed to the third order in the Amat-Nielsen classification. Twenty-two parameters related to the ground state and the dyad $\text{ν}{}_2\text{ν}{}_4$ have been transferred unchanged and 52 new parameters have been adjusted to fit experimental data, mainly interferometric ir data in the region 2250–3250 cm^?1. The analysis has been realized through J′ = 18 involving 1919 observed upper-state energies. The overall standard deviation of the fit is 0.022 cm^?1. A prediction of upper-state energies for the five bands has been carried out through J′ = 20. The model reproduces qualitatively and quantitatively the rotational fine structure of the upper levels in the full range of J′ values including level crossings (J′ ≥ 12), for the first time. The problem of higher excited vibrational states in methane is briefly discussed.     

Improved rovibrational constants and frequency tables for the normal laser bands of 12C16O2

New frequency difference measurements between Doppler-free stabilized laser lines in the 9.4- and 10.4-μm bands of ¹²C¹⁶O₂, including high-J and across-the-band-center measurements, have made significant improvements in the rovibrational constants. The absolute frequencies were referred to the methane stabilized 3.39-μm HeNe laser. Frequency tables generated from these constants have absolute uncertainties of less than two parts in 10¹⁰ and are about a factor of 10 better than older tables. In addition, the laser lines P_I(50) in ¹³C¹⁶O₂ and R_II(26) in ¹³C¹⁸O₂, which were used as reference lines in recent visible laser frequency measurements, were also measured to about the same accuracy.     

Interpretation of the 13C16O2 spectrum at 4.4 μm

The overlapping structure observed in the region of the ν₃ fundamental of ¹³C¹⁶O₂ at 4.4 μm has been assigned to several transitions belonging to not only the 13-C variety of carbon dioxide (¹³C¹⁶O₂) but also to ¹³C¹⁶O¹⁷O and ¹³C¹⁶O¹⁸O species occurring in the sample. Molecular constants have been evaluated for the assigned transitions.     

Strengths of single lines in the 12C16O2, ν3 band at 4.3 μm

Individual line strengths have been measured in the 4.3-μm ν₃ absorption band of ¹²C¹⁶O₂ from R46 to R90 using a vacuum grating spectrometer. Approximately 1100 measurements were made at pressures from 0.16 to 100.0 Torr, path lengths from 3.25 to 2331 cm, and temperatures from 246 to 338 K. The standard deviations of the measurements varied from 5 to 10%. The mean value of the vibrational dipole matrix element squared obtained is {R_if}² = 0.1103 ± 0.0085 D².     

The ν1 bands of 32S18O2 and 34S18O2 from infrared-microwave double resonance

Effective band constants for the ν₁ bands of both ³²S¹⁸O₂ and ³⁴S¹⁸O₂ have been determined from infrared-microwave double resonance spectroscopy. These results allow conclusions to be drawn over the processes involved in previously reported experiments with CO₂ lasers and oxygen-18 samples of SO₂.     

Identification and intensities of the “forbidden” 3ν23 band of 12C16O2

Lines of the 3ν₂³ “forbidden” band of ¹²C¹⁶O₂ have been identified in the 2000-cm^?1 region of a long-path, 0.01-cm^?1 resolution laboratory absorption spectrum. This band has detectable intensity due to Δl = 2 Fermi interactions between the upper level and the nearby ν₁ + ν₂ and 3ν₂¹ levels. Intensities of 18 lines of this band have been measured using a nonlinear least-squares spectral fitting technique. The intensities are enhanced at high J and an expression for the intensity distribution as derived by Toth [Appl. Opt.23, 1825–1834 (1984)] is used for the analysis. In terms of the total sample pressure, the vibrational band intensity is 0.194 ± 0.008 × 10^?30 cm^?1/molecule-cm^?2 at 296 K. The coefficient in the F factor is analogous to the Coriolis coefficient ξ and has been determined to be ?0.0413 ± 0.0015. As expected by theory, its value is very close to that of ξ for the related ν₁ + ν₂ band.     

A precise study of the rotational spectrum of formaldehyde H212C16O,H213C16O,H212C18O,H213C18O

The rotational spectra of formaldehyde, H₂¹²C¹⁶O and its isotopic species H₂¹³C¹⁶O, H₂¹²C¹⁸O, and H₂¹³C¹⁸O have been investigated in the ground vibrational state in the frequency region between 8 and 460 GHz. For most cases in which measurements of the a-type R- and Q-branch transitions already existed the accuracy of the line position has been improved to about 10 kHz. For H₂¹²C¹⁶O and H₂¹³C¹⁶O a large number of ΔK_a = ±2 transitions were measured with similar accuracy. These new data when combined with all other available data and appropriate weightings lead to a set of ground state parameters which for the first time are compatible with infrared and ultraviolet data. The rotational constants (and 3σ standard deviations) obtained using Watson's A-reduced Hamiltonian are:

     

14.

¹²CH₂F₂ and¹³CH₂F₂far-infrared lasers: New lines and frequency measurements     

S. C. Zerbetto  E. C. C. Vasconcellos  L. R. Zink  K. M. Evenson 《International Journal of Infrared and Millimeter Waves》1997,18(12):2301-2306

We report here the discovery of 13 new far-infrared laser lines from¹²CH₂F₂ and seven new lines from¹³CH₂F₂. Most of the new lines were pumped by high-J lines of the 9R branch of a cw-CO₂ laser. Wavelengths range from 97.6 to 616.18 μm. Frequency, pump offset, relative polarization, and relative intensity were measured for most of the new lines.     

15.

Acoustooptic extension of the frequency tunability of CW CO₂ lasers: New FIR lasers emissions from CH₃OH and¹³CH₃OH     

G. Carelli  N. Ioli  A. Moretti  G. Moruzzi  D. Pereira  F. Strumia 《International Journal of Infrared and Millimeter Waves》1991,12(5):449-471

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.     

16.

Assignments of fir laser emissions from CH₃OH optically pumped by an intra-cavity etalon tuned TEA-CO₂ laser     

Yoshio Nishi 《International Journal of Infrared and Millimeter Waves》1987,8(9):1189-1210

The author reports that TEA-CO₂ with an intra-cavity etalon is a useful pumping source which can deliver widely tunable beam (tunable range 1 GHz) with accurate oscillation frequencies and with high power compared to a tunable wave guide laser.The source is applied to the excitations of CH₃OH and the FIR emissions from it are well assigned for there absorption transitions and FIR emissions. This proves that the source display not only usefulness for development of new FIR emissions but also for molecular spectroscopy.     

17.

¹²C¹⁶O₂: Σ and Π Fermi dyads in the 4.5-μm region: Wavenumbers and spectroscopic constants     

D. Bailly  C. Rossetti 《Journal of Molecular Spectroscopy》1983,102(2):392-398

Emission spectra of CO₂ vibrationally excited by a dc electric discharge were recorded under Doppler-limited resolution, using the high information interferometer of Laboratoire d'Infrarouge Orsay, France, in the spectral region 4–5 μm. Sixteen bands with Δv₃ = 1 of ¹²C¹⁶O₂ involving the Fermi dyads (10⁰v₃, 02⁰v₃)_{I and II} and (11¹v₃, 03¹v₃)_{I and II} have been studied. The band centers and the spectroscopic constants for all the vibrational levels involved are given. They reproduce the experimental wavenumbers with a rms of the order of 4 × 10^?5 cm^?1 for the best vibrational transition and always less than 3 × 10^?4 cm^?1 for the others. These results are compared with laser measurements for the (10⁰0, 02⁰0) dyad.     

18.

Submillimeter emission lines from CD₂Cl₂ optically pumped lasers     

P. Belland  M. Fourrier 《International Journal of Infrared and Millimeter Waves》1986,7(8):1251-1256

Fifty-five new submillimeter laser lines from optically pumped CD₂Cl₂, have been obtained in a FIR metallic waveguide resonator. Twenty-seven lines, ranging from 184 m to 1387 m, and twenty-eight lines, from 219 m to 888 m, have been observed when using CW CO₂ laser and CW N₂O laser optical pumping, respectively. The accuracy of wavelength measurements are of the order of 3.10^–3.     

19.

Absolute intensities and pressure broadening coefficients measured at different temperatures for the 201_II ← 000 band of ¹²C¹⁶O₂ at 4978cm^-1     

Francisco P.J. Valero  Carlos B. Suarez  Robert W. Boese 《Journal of Quantitative Spectroscopy & Radiative Transfer》1980,23(3):337-341

Absolute line intensities and self-broadening coefficients have been measured at 197° and 294°K for the 201_II ← 000 band of ¹²C¹⁶O₂ at about 4978cm^-1. The vibration-rotation factor (F_VR), the purely vibrational transition moment (∣R(O)∣), and the integrated band intensity (S_band) are deduced from the measurements. The results are: F_VR(m)=1+(0.24±0.08)x10^-4m+(0.55+0.21)x10^-4m², ∣R(O)∣= (4.340±0.008x10^-3 debye, S_band=96372±190cm^-1km^-1atm^-1_STP. The results for self-broadening coefficients, as well as for individual vibration-rotation lines, are presented in the text.     

20.

The infrared spectra of ¹²C³²S, ¹²C³⁴S, ¹³C³²S,and ¹²C³³S     

Terry R. Todd  Wm.Bruce Olson 《Journal of Molecular Spectroscopy》1979,74(2):190-202

Using a tunable diode laser spectrometer, the infrared absorption spectra of four isotopic species of carbon monosulfide have been observed in the positive column of a dc discharge of CS₂ and Ar. The wavenumbers of 115 vibration-rotation transitions between 1180.5 and 1266.1 cm^?1 have been measured. These lines were assigned to the 1-0, 2-1, 3-2, and 4-3 bands of ¹²C³²S, the 1-0 and 2-1 bands of ¹²C³⁴S and ¹³C³²S, and the 1-0 band of ¹²C³³S. These new data have been combined with the previous infrared and microwave results to determine Dunham coefficients (Y_ij), the Dunham potential expansion constants (a₀,a₁,a₂,a₃, and a₄), and the classical turning points by the RKR method.     

	H212C16O	H213C16O	H212C18O	H213C18O
A/MHz	281 970.572 (24)	281 993.258(135)	281 961.94 (39)	281 985.00 (93)
B/MHz	38 836.0456(13)	37 811.0887(25)	36 904.1693(66)	35 859.256(10)
C/MHz	34 002.2034(12)	33 213.9790(25)	32 511.5311(63)	31 697.868(10)

12CH2F2 and13CH2F2far-infrared lasers: New lines and frequency measurements

We report here the discovery of 13 new far-infrared laser lines from¹²CH₂F₂ and seven new lines from¹³CH₂F₂. Most of the new lines were pumped by high-J lines of the 9R branch of a cw-CO₂ laser. Wavelengths range from 97.6 to 616.18 μm. Frequency, pump offset, relative polarization, and relative intensity were measured for most of the new 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.     

Assignments of fir laser emissions from CH3OH optically pumped by an intra-cavity etalon tuned TEA-CO2 laser

The author reports that TEA-CO₂ with an intra-cavity etalon is a useful pumping source which can deliver widely tunable beam (tunable range 1 GHz) with accurate oscillation frequencies and with high power compared to a tunable wave guide laser.The source is applied to the excitations of CH₃OH and the FIR emissions from it are well assigned for there absorption transitions and FIR emissions. This proves that the source display not only usefulness for development of new FIR emissions but also for molecular spectroscopy.     

12C16O2: Σ and Π Fermi dyads in the 4.5-μm region: Wavenumbers and spectroscopic constants

Emission spectra of CO₂ vibrationally excited by a dc electric discharge were recorded under Doppler-limited resolution, using the high information interferometer of Laboratoire d'Infrarouge Orsay, France, in the spectral region 4–5 μm. Sixteen bands with Δv₃ = 1 of ¹²C¹⁶O₂ involving the Fermi dyads (10⁰v₃, 02⁰v₃)_{I and II} and (11¹v₃, 03¹v₃)_{I and II} have been studied. The band centers and the spectroscopic constants for all the vibrational levels involved are given. They reproduce the experimental wavenumbers with a rms of the order of 4 × 10^?5 cm^?1 for the best vibrational transition and always less than 3 × 10^?4 cm^?1 for the others. These results are compared with laser measurements for the (10⁰0, 02⁰0) dyad.     

Submillimeter emission lines from CD2Cl2 optically pumped lasers

Fifty-five new submillimeter laser lines from optically pumped CD₂Cl₂, have been obtained in a FIR metallic waveguide resonator. Twenty-seven lines, ranging from 184 m to 1387 m, and twenty-eight lines, from 219 m to 888 m, have been observed when using CW CO₂ laser and CW N₂O laser optical pumping, respectively. The accuracy of wavelength measurements are of the order of 3.10^–3.     

Absolute intensities and pressure broadening coefficients measured at different temperatures for the 201II ← 000 band of 12C16O2 at 4978cm-1

Absolute line intensities and self-broadening coefficients have been measured at 197° and 294°K for the 201_II ← 000 band of ¹²C¹⁶O₂ at about 4978cm^-1. The vibration-rotation factor (F_VR), the purely vibrational transition moment (∣R(O)∣), and the integrated band intensity (S_band) are deduced from the measurements. The results are: F_VR(m)=1+(0.24±0.08)x10^-4m+(0.55+0.21)x10^-4m², ∣R(O)∣= (4.340±0.008x10^-3 debye, S_band=96372±190cm^-1km^-1atm^-1_STP. The results for self-broadening coefficients, as well as for individual vibration-rotation lines, are presented in the text.     

The infrared spectra of 12C32S, 12C34S, 13C32S,and 12C33S

Using a tunable diode laser spectrometer, the infrared absorption spectra of four isotopic species of carbon monosulfide have been observed in the positive column of a dc discharge of CS₂ and Ar. The wavenumbers of 115 vibration-rotation transitions between 1180.5 and 1266.1 cm^?1 have been measured. These lines were assigned to the 1-0, 2-1, 3-2, and 4-3 bands of ¹²C³²S, the 1-0 and 2-1 bands of ¹²C³⁴S and ¹³C³²S, and the 1-0 band of ¹²C³³S. These new data have been combined with the previous infrared and microwave results to determine Dunham coefficients (Y_ij), the Dunham potential expansion constants (a₀,a₁,a₂,a₃, and a₄), and the classical turning points by the RKR method.