ICLAS of weak transitions of water between 11 300 and 12 850 cm: Comparison with FTS databases

Very weak water vapor absorption lines have been investigated by intracavity laser absorption spectroscopy (ICLAS) in the 11 335-11 947 and 12 336-12 843 cm⁻¹ spectral regions dominated by the ν₁ + 3ν₂ + ν₃ and ν₂ + 3ν₃ bands, respectively. A detectivity on the order of α_min ∼ 10⁻⁹ cm⁻¹ was achieved with an ICLAS spectrometer based on a Ti: Sapphire laser. It allowed detecting transitions with an intensity down to 5 × 10⁻²⁸ cm/molecule which is about 10 times lower than the weakest line intensities previously detected in the considered region. A line list corresponding to 1281 transitions with intensity lower than 5 × 10⁻²⁶ cm/molecule has been generated. A detailed comparison with the line lists provided by the HITRAN database and by recent investigations by Fourier transform spectroscopy associated with very long multi pass cell is presented. The rovibrational assignment performed on the basis of the ab initio calculations of Schwenke and Partridge, has allowed for determining 176 new energy levels belonging to a total of 16 vibrational states.     

束-气条件下He(23S)与CH3Cl及CH3I的传能研究

在束-气条件下，通过检测产物的化学发光，研究了亚稳电子激发态He（23S）原子与CH3Cl、CH3I传能反应.采用参比反应的方法，测得了由上述反应产生的主要碎片CH（A2△）、CH（B2∑-）、CH（C2∑+）和H*形成速率常数．通过对测得的CH（A2△－X2∏r）和CH（B2∑-－X2∏r）色散谱进行计算机模拟，获得了初生态的CH（A2△，v＝0－2）和CH（B2∑-，v＝0态）的振动-转动布居，实验结果表明，CH（A2△，v＝0）态的转动布居是呈双Boltzman分布的，并且反应的可资用能大部分将转变成产物的平动能．根据实验结果和反应阈能的分析，本文对He（23S）与CH3Cl／CH3I传能反应机理进行了探讨。     

High sensitivity CW-Cavity Ring Down Spectroscopy of N2O near 1.5 μm (II)

We present the second part of the investigation of the high sensitivity absorption spectrum of nitrous oxide by CW-Cavity Ring Down Spectroscopy near 1.5 μm. In a first paper [A.W. Liu, S. Kassi, P. Malara, D. Romanini, V.I. Perevalov, S.A. Tashkun, S.M. Hu, A. Campargue, J. Mol. Spectrosc. 244 (2007) 33-47] devoted to the 6000-6833 cm⁻¹ region, more than 6000 line positions of five isotopologues (¹⁴N₂¹⁶O, ¹⁵N¹⁴N¹⁶O, ¹⁴N¹⁵N¹⁶O, ¹⁴N₂¹⁷O, and ¹⁴N₂¹⁸O), were rovibrationally assigned to a total of 68 bands. The achieved noise equivalent absorption (α_min ∼ 2 × 10⁻¹⁰ cm⁻¹) allowed for the detection of lines with intensity weaker than 2 × 10⁻²⁹ cm/molecule. In this contribution, the investigated region was extended down to 5905 cm⁻¹ and additional recordings allowed accessing small spectral sections uncovered in our preceding recordings. A deeper analysis based on the predictions of the effective Hamiltonian model has allowed assigning a total of 3149 transitions and lowering the percentage of lines left unassigned from 51% to 28%. It led to the analysis of 35, 6, 7, and 6 bands for the ¹⁴N₂¹⁶O, ¹⁵N¹⁴N¹⁶O, ¹⁴N¹⁵N¹⁶O, and ¹⁴N₂¹⁸O isotopologues, respectively. Forty-two of these 54 bands are newly observed, while the rotational analysis of the twelve others is significantly extended and improved. Most of the bands were found unperturbed and their line positions could be reproduced within the experimental uncertainty (about 1 × 10⁻³ cm⁻¹). The corresponding spectroscopic parameters are reported. Local rovibrational perturbations induced by either intrapolyad or interpolyad couplings were found to affect five hot bands of ¹⁴N₂¹⁶O. Their detailed analysis is presented.     

The ν12 band of C2D4

The Fourier transform infrared (FTIR) absorption spectrum of the ν₁₂ fundamental band of ethylene-d₄ (C₂D₄) was recorded in the 1017-1137 cm⁻¹ region with an unapodized resolution of 0.0063 cm⁻¹. Upper state (v₁₂ = 1) rovibrational constants consisting of three rotational and five quartic constants were improved by assigning and fitting 2103 infrared transitions using Watson’s A-reduced Hamiltonian in the I^r representation. The band centre of the A-type ν₁₂ band is found to be 1076.98480 ± 0.00002 cm⁻¹. The present analysis covering a wider wavenumber range and higher J and K_c values yielded upper state constants including the band centre which are more accurate than previously reported. The rms deviation of the upper state fit is 0.00045 cm⁻¹. Improved ground state rovibrational constants were also determined from the fit of 1247 ground state combination differences (GSCD) from the presently-assigned infrared transitions of the ν₁₂ band of C₂D₄. The rms deviation of the GSCD fit is 0.00049 cm⁻¹. In the rovibrational analysis, local frequency perturbations were not detected even at high J and K_a values. The calculated inertial defect Δ₁₂ is 0.32551 ± 0.00001 μŲ. The line intensities of the individual transitions in the ν₁₂ band were measured and the band strength of 39.8 ± 2.0 cm⁻² atm⁻¹ was derived for the ν₁₂ band of C₂D₄.     

The absorption spectrum of water between 13 540 and 14 070 cm: ICLAS detection of weak lines and a complete line list

The absorption spectrum of water vapor has been investigated by Intracavity Laser Absorption Spectroscopy (ICLAS) between 13 540 and 14 070 cm⁻¹. This spectrum is dominated by relatively strong transitions of the 4δ polyad of vibrational states. The achieved sensitivity - on the order of α_min ∼ 10⁻⁹ cm⁻¹ - has allowed one to newly measure 222 very weak transitions with intensities down to 5 × 10⁻²⁸ cm/molecule at 296 K. Fifty new or corrected H₂¹⁶O energy levels belonging to a total of 13 vibrational states could be determined from the rovibrational analysis based on variational calculations by Schwenke and Partridge. The previous investigations in the region by Fourier Transform Spectroscopy were critically evaluated and used to construct the best to date set of energy levels accessed by transitions in the considered region. All the rovibrational transitions reaching these upper energy levels and having intensities larger than 4.0 × 10⁻²⁸ cm/mol were calculated. In the resulting line list, the positions at the level of experimental accuracy were augmented with variational intensities leading to the most complete line list for water in normal isotopic abundance in the 13 500-14 100 cm⁻¹ region.     

Rovibrational spectrum and potential energy surface of the N2-N2O van der Waals complex

The rovibrational spectrum of the N₂-N₂O van der Waals complex has been recorded in the N₂O ν₁ region (∼1285 cm⁻¹) using a tunable diode laser spectrometer to probe a pulsed supersonic slit jet. The observed transitions together with the data observed previously in the N₂O ν₃ region are analyzed using a Watson S-reduced asymmetric rotor Hamiltonian. The rotational and centrifugal distortion constants for the ground and excited vibrational states are accurately determined. The band-origin of the spectrum is determined to be 1285.73964(14) cm⁻¹. A restricted two-dimensional intermolecular potential energy surface for a planar structure of N₂-N₂O has been calculated at the CCSD(T) level of theory with the aug-cc-pVDZ basis sets and a set of mid-bond functions. With the intermolecular distance fixed at the ground state value R = 3.6926 Å, the potential has a global minimum with a well depth of 326.64 cm⁻¹ at θ_N2 = 11.0° and θ_N2O = 84.3° and has a saddle point with a barrier height of 204.61 cm⁻¹ at θ_N2 = 97.4° and θ_N2O = 92.2°, where θ_N2(θ_N2O) is the enclosed angle between the N-N axis (N-N-O axis) and the intermolecular axis.     

Combined analysis of the high sensitivity Fourier transform and ICLAS-VeCSEL absorption spectra of D2O between 8800 and 9520 cm

The absorption spectrum of dideuterated water, D₂O, has been recorded between 8800 and 9520 cm⁻¹ by intracavity laser absorption spectroscopy (ICLAS) based on a vertical external cavity system emitting laser (VeCSEL) and by high sensitivity Fourier Transform spectroscopy. The combined analysis of the spectra has allowed attributing 1223 transitions to the D₂O species. The spectrum assignment was performed on the basis of the recent results of variational calculations based on an optimized potential energy surface of D₂O. A set of 687 energy levels was derived from transitions assigned to eight upper vibrational states, 577 of them being reported for the first time. A detailed line list has been generated. The line intensities were retrieved mainly from the FTS spectrum and the absolute integrated intensities of the 2v₁ + v₂ + v₃ and the v₂ + 3v₃ bands dominating the spectrum have been determined.     

Near infrared emission spectrum of HCN

The emission spectrum of H¹³CN at 1370 K has been recorded with a hot gas high resolution FT-IR emission apparatus [1] in the wavenumber region of with a resolution of . This work reports the analysis of 50 subbands for the H¹³CN isotopologue of hydrogen cyanide in the 2ν₁ wavenumber region. 23 rovibronic states of H¹³CN including the rovibronic states at have been characterized for the first time and for seven other states it was possible to improve the existing spectroscopic constants substantially. The dense emission spectrum was analyzed with the spectrum analysis software SyMath™ implemented in the Mathematica™ computer algebra system [1].     

Rovibrational spectrum of the Ne-N2O van der Waals complex in the 1285 cm region

The rovibrational spectrum of the Ne-N₂O van der Waals complex has been recorded in the symmetric stretching mode region of the N₂O monomer (∼1285 cm⁻¹) using a tunable diode laser spectrometer in conjunction with an astigmatic multi-pass cell and a pulsed supersonic slit jet. The spectra of both ²⁰Ne-N₂O and ²²Ne-N₂O isotopomers are assigned and analyzed using a Watson S-reduced asymmetric-rotor Hamiltonian. The rotational and centrifugal constants for the excited vibrational state are accurately determined. The band-origin of the spectrum is determined to be ν₀ = 1285.12251(18) cm⁻¹ for ²⁰Ne-N₂O and 1285.12363(27) cm⁻¹ for ²²Ne-N₂O, which shows a blue-shift of 0.21921 cm⁻¹ for ²⁰Ne-N₂O and 0.22033 cm⁻¹ for ²²Ne-N₂O from that of the N₂O monomer, respectively.     

High resolution analysis of the rotational levels of the (0 0 0), (0 1 0), (1 0 0), (0 0 1), (0 2 0), (1 1 0) and (0 1 1) vibrational states of SO2

A high resolution (0.0018 cm⁻¹) Fourier transform instrument has been used to record the spectrum of an enriched ³⁴S (95.3%) sample of sulfur dioxide. A thorough analysis of the ν₂, 2ν₂ − ν₂, ν₁, ν₁ + ν₂ − ν₂, ν₃, ν₂ + ν₃ − ν₂, ν₁ + ν₂ and ν₂ + ν₃ bands has been carried out leading to a large set of assigned lines. From these lines ground state combination differences were obtained and fit together with the existing microwave, millimeter, and terahertz rotational lines. An improved set of ground state rotational constants were obtained. Next, the upper state rotational levels were fit. For the (0 1 0), (1 1 0) and (0 1 1) states, a simple Watson-type Hamiltonian sufficed. However, it was necessary to include explicitly interacting terms in the Hamiltonian matrix in order to fit the rotational levels of the (0 2 0), (1 0 0) and (1 0 1) states to within their experimental accuracy. More explicitly, it was necessary to use a ΔK = 2 term to model the Fermi interaction between the (0 2 0) and (1 0 0) levels and a ΔK = 3 term to model the Coriolis interaction between the (1 0 0) and (0 0 1) levels. Precise Hamiltonian constants were derived for the (0 0 0), (0 1 0), (1 0 0), (0 0 1), (0 2 0), (1 1 0) and (0 1 1) vibrational states.