Laser-radiofrequency double-resonance spectroscopy of 13CH3I

Pure quadrupole resonances of the I¹²⁷ nucleus of ¹³CH₃I have been observed using laser-radiofrequency double resonance. Quadrupole coupling constants are reported for the ground, ν₃, 2ν₃, ν₆, 2ν₆, ν₃ + ν₆, and 2ν₃ + 2ν₆ states. Smaller hyperfine constants are also reported for the ground and ν₆ states.     

Further new CW FIR lasting investigations in CH3I,13CH3I and CD3I: New lines and assignments

Forty seven new CW FIR emissions lines have been observed in CH₃I,¹³CH₃I and CD₃I, optically pumped by a CO₂ laser and a N₂ laser, in a metallic waveguide resonator. Assignments are given for a large number of these new lines.     

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.     

CH3I: Isotope shift for 129I in the v6 band

The isotope shift in the v₆ band of CH₃I has been measured with high resolution for the radioisotope ¹²⁹I (half-life = 1.6 × 10⁷ y) with respect to the stable ¹²⁷I, using tunable diode laser spectroscopy. The average shift obtained from 30 transitions, free from interference in the ^RQ(J, 3) and ^RQ(J, 4) branches, amounted to (-0.0135 ± 0.0006) cm^-1. The abundance ratio ¹²⁹I/¹²⁷I in the gas mixture was determined spectroscopically on ^RQ(16, 3) and found to be (0.032 ± 0.003), as compared to a mass-spectrometric analysis of (0.030 ± 0.001). The self and air broadening coefficients measured on ^RR(6, 0) of CH₃¹²⁷I were (32 ± 3) MHz Torr^-1 and (10.4 ± 1.5) MHz Torr^-1 respectively. The line strengths for ^RQ(16, 3) were found to be (2.0 ± 0.2) × 10^-21 cm^-1 mol^-1 cm² for both CH₃¹²⁷I and CH₃¹²⁹I.     

Spectral intensities in the ν3 bands of 12CH4 and 13CH4

Relative and absolute line intensities for the ν₃ bands of the ¹²C and ¹³C isotopic varieties of methane have been measured using a tunable difference-frequency laser spectrometer. From these data the integrated band strength of ¹³CH₄ is calculated to be 0.983 ± 0.007 that of ¹²CH₄, with the uncertainty representing three standard deviations. The absolute ν₃ bandstrength for ¹²CH₄ is 266.1 ± 3.0 cm^?2 atm ^?1 at 294.7 K where the errors are dominated by the pressure measurement. This band strength corresponds to an effective transition moment 〈μ₃〉 = 0.0534(3)D for ¹²CH₄ from which the ν₄ band dipole moment and the Herman-Wallis F factor can be estimated using a recent force field model for methane.     

Intensities of the v1-bands of 12CH335Cl and 12CH337Cl near 3 μm

Strengths of individual lines in the v₁ fundamental of methyl chloride have been measured at low pressure and at 296.35 K using a Fourier transform interferometer. The band strengths S_v⁰ obtained by fitting these measurements are 85.8±1.0 and 86.6±1.0 cm^-2 atm^-1 for ¹²CH₃³⁵Cl and ¹²CH₃³⁷Cl, respectively. The Q₃-branch appears to be useful for atmospheric detection of methyl chloride.     

High-resolution diode laser spectra of the ν4 mode of 12CF3I and 13CF3I

High-resolution spectra of the ν₄ mode of ¹²CF₃I and ¹³CF₃I have been recorded using diode laser spectroscopic techniques. The sample was cooled to 163 ± 10 K to suppress the hot bands. Natural CF₃I containing 98.9% ¹²CF₃I and 1.1% ¹³CF₃I was used for recording the spectra. About 1200 lines in the P and R branches of each isotopic molecule have been assigned and used in the least-squares fit. The pseudoparallel structure of the bands has been understood and accurate values of rotational constants have been obtained.     

13CH3F and12CH3 mixture FIR Raman lasar

Experimental results of the investigation of¹³CH₃F and¹²CH₃F isotopic mixture as an active medium of optically pumped FIR laser are presented. The experimental data of the output FIR and MIR radiation are given.     

Diode laser spectroscopy of the ν6 band of 13CH3l and the ν″6 band of 12CH2Dl

The ν₆ band of ¹³CH₃I and the ν″₆ band of ¹²CH₂DI have been recorded under Doppler-limited resolution in the region 820–866 cm^?1 using a tunable diode laser spectrometer. For ¹³CH₃I the constants for the ν₆ band were determined by simultaneous analysis of seven ^pQ(J,K) branches and several ^pP(J,K) and ^pR(J,K) transitions. For ¹²CH₂DI, the slight asymmetry introduced by the single D atom gives rise to noticeable asymmetry effects in the spectra of some of the ^pQ(J,K) subbands. From the analysis of six such subbands, the molecular constants for the ν″₆ level were determined.     

Analysis of the ν2 + ν3 band of 12CH4 and 13CH4

The ν₂ + ν₃ bands of ¹²CH₄ and ¹³CH₄ occurring in the region 4400–4650 cm^?1 have been studied from spectra recorded with a high-resolution Fourier transform spectrometer (resolution better than 0.01 cm^?1). Champion's Hamiltonian expansion, Canad. J. Phys.55, 1802 (1977), is applied to the problem of the two interacting F₁ and F₂ vibrational sublevels of this type of a band. As the P branch of ν₂ + ν₃ is strongly overlapped by neighboring bands, a combination-difference method, adapted to tetrahedral XY₄ molecules has been developed to help assignments of lines. A fit of 700 transitions has been performed using 13 new effective constants in the case of ¹²CH₄. In the case of ¹³CH₄, 532 transitions have been fit to 18 constants. The known parameters, relative to the vibrational ground state and the ν₃ state for both methanes, and the ν₂ state for ¹²CH₄ were fixed throughout. Most of the perturbed levels, up to J′ = 12, are well reproduced and the general agreement between experimental and calculated transitions is satisfactory with standard deviations of 0.047 cm^?1 (¹²CH₄) and 0.041 cm^?1 (¹³CH₄). The results (order of magnitude of obtained (ν₂ + ν₃) parameters and comparison of observed and computed intensities) indicate that the ν₂ + ν₃ band is perturbed by many other bands.     

Microwave measurements and calculations of quadrupole coupling effects in CH3I and CD3I

The transitions J = 1 ← 0, K = 0; J = 2 ← 1, K = 0; and J = 2 ← 1, K = 1 of CH₃I and CD₃I were measured using a Stark-modulated microwave spectrometer. Iodine quadrupole coupling strengths were analyzed to determine variations with deuterium substitution on the methyl group and variations with centrifugal distortion. Quadrupole coupling strengths were described by the expression $\text{eQq}{}_0\text{+ aJ(J + 1) + bK}{}^2\text{+}\text{cK}{}^4\text{J(J + 1)}$. Explicit expressions are given for a, b, and c for a symmetric top in terms of molecular parameters. For CH₃I eQq₀ = ?1934.11 ± 0.02 MHz and for CD₃I eQq₀ = ?1928.95 ± 0.04 MHz. Rotational constants obtained are B(CH₃I) = 7501.274 ± 0.002 MHz and B(CD₃I) = 6040.298 ± 0.007 MHz. The observed fractional change in halogen quadrupole coupling of 0.0027 is related to previous results for methyl chloride and methyl bromide.     

Rotational and hyperfine constants of CD3I

The rotational spectra of CD₃I (v = 0; v₃ = 1; v₆ = 1) and of ¹³CD₃I in its ground state were observed between 8 and 320 GHz. For the ground state of CD₃I, pure quadrupole resonances were also measured by laser-radiofrequency double resonance. These data have been used to determine with high accuracy the rotational, centrifugal distortion, and hyperfine constants.     

The torsion-rotation microwave spectrum of 12CH318OH and the structure of methanol

The microwave and millimeter wave spectrum of ¹²CH₃¹⁸OH has been observed in the frequency region 7.9–200 GHz. Both a- and b-type transitions have been assigned and measured. This spectrum was analyzed using the method of Lees and Baker, and rotational constants, torsional constants, centrifugal distortion constants, the barrier to internal rotation and moments of inertia have been evaluated. The barrier has been found to be 374.91 ± 0.18 cm^?1, in good agreement with that of ¹²CH₃¹⁶OH. The moments of inertia were combined with those of other isotopic species to give a full substitution structure. To assist searches for this molecule in interstellar space a table of predicted frequencies of astrophysically interesting transitions is presented.     

Diode laser spectroscopy of the ν6 band of 12CH3I

The vibration-rotation spectrum of the ν₆ fundamental of methyl iodide has been recorded in the 824 to 862 cm^?1 region by using a tunable semiconductor diode laser spectrometer. The rotational analysis performed for six Q branches ^pQ(J,3), ^pQ(J,4), ^pQ(J,5), ^pQ(J,6), ^pQ(J,7), and ^qQ(J,8) led to accurate values for several molecular constants. The nuclear quadrupole splitting arising from the spin of iodine has been observed very clearly in the low J transitions and for various K values.     

Microwave and submillimeterwave spectra of CH2DI and CHD2I

The pure rotational spectra of CH₂DI and CHD₂I have been measured by microwave Fourier transform spectroscopy, millimeterwave spectroscopy and submillimeterwave spectroscopy. The quadrupole hyperfine structure due to iodine has been analyzed by direct diagonalization of the quadrupole tensor. For the J = 1-0 transition of the ground state of CH₂DI, the quadrupole hyperfine structure due to deuterium could be resolved and the quadrupole coupling constant eQq_aa(D) determined.Accurate rotational and centrifugal distortion constants (up to sextic terms) have been determined. They are compared to the constants derived from the ground state combination differences (GSCD). A good agreement is observed but it is also found that the two kinds of data (GSCD and microwave) are complementary and a combined fit allows us to significantly improve the accuracy of the constants.     

Ground-state rotational constants of 13CH3D

An analysis of the ground-state combination differences in the ν₂(A₁) band of ¹³CH₃D (ν₀ = 2190.0485 cm^?1) has been made to yield accurate values for six ground-state rotational constants, B₀, D₀^J, D₀^JK, H₀^JJJ, H₀^JJK, and H₀^JKK.     

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.     

(CH3I)n(n=1,2,3,4)的同步辐射光电离研究

用VUV同步辐射辐照在连续的超声射流冷却束中产生的（CH₃I)_n（n=1,2，3，4）团簇分子，通过测量其光电离及解离电离产生的各种离子的光电离效率（PIE）曲线，获得了（CH₃I)_n⁺（n=1，2，3，4）的绝热电离势及各种碎片离子的出现势，估算了有关分子的键能．在CH₃I⁺的PIＥ曲线上观察到CH₃I分子的自电离结构，并对其进行了标识，归属为收敛于CH₃I⁺（²E_1/2）态的4组Rydberg系，即ns，npσ，npπ和nd． 关键词：     

The rotation-vibration constants of the 12CH3F ν3 band

Accurate rotational and vibrational constants for the ground and the ν₃ states of ¹²CH₃F are derived from a simultaneous least-squares fit of all the previous microwave, laser Stark and far-infrared laser data related to the ν₃ ← 0 band. Spectroscopic data, concerning the far-infrared laser emission in ¹²CH₃F, are discussed.     

The pure rotational spectrum of Difluoroiodomethane, CHF2I

The pure rotational spectrum of CHF₂I has been recorded for the first time, in a supersonic expansion in the region 1.7-17 GHz, and at room-temperature in the region 302-318 GHz. The observed transitions span the values of J^″ from 0 up to 67. Precise rotational and centrifugal distortion constants have been determined. Furthermore, the complete iodine nuclear electric quadrupole coupling tensor, in the inertial and principal axes, has been determined. Quantum chemical calculations have been performed to aid with the analysis. Iodine quadrupole mediated perturbations have resulted in the following observations: (i) several transitions having enhanced intensities and (ii) the observation of several forbidden, ΔJ=±2, transitions. Comparisons in electronic structure are made between the series of molecules CH_3-nF_nX; and X = Cl, Br, I.