High resolution study of the ν5 + ν12 band of C2H4

The combination band ν₅ + ν₁₂ of ethylene, C₂H₄, has been recorded for the first time with a high resolution Fourier transform spectrometer Bruker IFS 125HR. Assignments of transitions and preliminary rotational analysis are made. Two models (Hamiltonian of the isolated vibrational state and Hamiltonian that takes into account resonance interactions) are used. Influence of the local resonance interactions on the parameters and reproduction power of the models is discussed.     

High-resolution investigation of the weak ν1+3ν21-ν21+ν3 band of CO2 around 2 μm

Fundamental spectroscopical parameters of the weak ν₁+3ν₂ ¹-ν₂ ¹+ν₃ band of CO₂ are reported using a high-resolution, direct-absorption spectrometer, based on a distributed feed-back diode laser emitting at 2 μm. Line intensities and self-broadening coefficients have been measured for the first time with high accuracy, for nine lines of the R branch, from R(44) up to R(59). Comparison with available data has been made, and a generally good agreement has been found. Received: 30 August 1999 / Published online: 24 March 2000     

Detection of HCl on the first and second overtone using semiconductor diode lasers at 1.7 μm and 1.2 μm

Sensitivity studies are also performed, to evaluate the minimum detectable concentration of HCl in air. Received: 7 August 1998/Revised version: 5 October 1998     

Diode laser spectroscopy of the ν1-ν3 band of CF335Cl at 15.84 μm

The vibration-rotation spectrum of CF₃Cl, with natural isotopic abundance, has been recorded in the 622- to 641-cm⁻¹ region using a tunable diode laser spectrometer. The K structure of many P(J) and R(J) manifolds of the ν₁-ν₃ difference band of CF₃³⁵Cl has been resolved and positively identified. The rotational analysis has been extended in the P and R branches up to J = 39 and 47, respectively, and more than 650 lines have been assigned. A least-squares fit of the observed transitions to the energy expression including the quartic centrifugal distortion terms was performed and molecular constants for the ν₁-ν₃ difference band were determined. From the obtained parameters the ν₃ band center of CF₃³⁵Cl was evaluated as 476.9750(4) cm⁻¹ and the values of α₃^A and α₃^B were derived to be 50(1) × 10⁻⁶ and 82.9(6) × 10⁻⁶ cm⁻¹, respectively.     

Rotational analysis of the ν2 band of NH2D

High-resolution diode laser spectra and medium-resolution F-T spectra of deuterated ammonia have been obtained in the 700- to 1030-cm⁻¹ region. Out of about 800 lines measured by diode laser spectroscopy, approximately 500 lines have been assigned to the ν₂ transitions of NH₂D. The parameters for the ground and ν₂ states of NH₂D have been derived by the simultaneous analysis of the infrared and microwave data. The standard deviation for the IR data is ∼8 × 10⁻⁴ cm⁻¹. It is shown that the energy levels of NH₂D in the ν₂ state are heavily perturbed by inversion-rotation interaction and that it is necessary to include higher order inversion-rotation interaction terms to obtain a satisfactory fit of the observed data.     

Low-temperature high-resolution absorption spectrum of 14NH3 in the ν1+ν3 band region (1.51 μm)

Jet-cooled spectra of ¹⁴NH₃ and ¹⁵NH₃ in natural abundance were recorded using cavity ring-down (CRDS, 6584–6670 cm^?1) and cavity enhanced absorption (CEAS, 6530–6700 cm^?1) spectroscopy. Line broadening effects in the CRDS spectrum allowed lines with J ^″-values between 0 and 3 to be identified. Intensity ratios in ¹⁴NH₃ between the jet-cooled CRDS and literature room-temperature data from Sung et al. (J. Quant. Spectrosc. Radiat. Transfer, 113 (2012 K. Sung , L.R. Brown , X. Huang , D.W. Schwenke , T.J. Lee , S.L. Coy , and K.K. Lehmann , J. Quant. Spectrosc. Radiat. Transfer 113 , 1066 (2012).[Crossref], [Web of Science ®] , [Google Scholar]), 1066) further assisted the line assignments. Ground state combination differences were extensively used to support the assignments, providing reliable values for J, K and inversion symmetry of the ground state vibrational levels. CEAS data helped in this respect for the lowest J lines, some of which are saturated in the CRDS spectrum. Further information on a/s doublets arose from the observed spectral structures. Thirty-two transitions of ¹⁴NH₃ were assigned in this way and a limited but significant number (19) of changes in the assignments results, compared to Sung et al. or to Cacciani et al. (J. Quant. Spectrosc. Radiat. Transfer, 113 (2012 P. Cacciani , P. Cermak , J. Cosleou , M. Khelkhal , P. Jeseck , and X. Michaut , J. Quant. Spectrosc. Radiat. Transfer 113 , 1084 (2012).[Crossref], [Web of Science ®] , [Google Scholar]), 1084). Sixteen known and 25 new low-J transitions were identified for ¹⁵NH₃ in the CRDS spectrum but the much scarcer literature information did not allow for any more refined assignment. The present line position measurements improve on literature values published for ¹⁵NH₃ and on some line positions for ¹⁴NH₃.     

Laser Stark spectroscopy; a case study in the ν2 fundamental band of 14NH3

The ν₂ fundamental band of ¹⁴NH₃ is observed with a laser Stark spectrometer in Doppler-limited resolution. A set of 41 constants including the electric dipole moment and its rotational dependence are determined from 360 Stark resonances observed in the present work and 67 millimeter- and submillimeter-wave inversion and rotation-inversion lines reported in the literature. The rms residual of the fit is 3.1 × 10⁻⁴ cm⁻¹. Field-free transition frequencies of the band in the region 800–1160 cm⁻¹ are calculated from the constants and tabulated together with their estimated uncertainties and relative absorption intensities. Rotational dependence of the electric dipole matrix elements of a C_3v molecule is presented on the basis of the conventional theory of vibration-rotation.     

Spectroscopic properties of 1.8 μm emission of thulium ions in germanate glass

A new type host of germanate glass (GeO₂− BaO−BaF₂−Ga₂O₃−La₂O₃) codoped with Tm₂O₃ has been investigated for application as laser material. It possesses a large emission cross section with the value of 9.3×10⁻²¹ cm² at 1.8 μm. Judd-Ofelt intensity parameters and radiative transition probability are calculated and analyzed by Judd-Ofelt theory and absorption spectra. The infrared emission spectra at 1.8 μm have been obtained by using a 794 nm laser diode as excitation resource. The emission intensity ratio of 1.8 (³F₄→³H₆) to 1.47 μm (³H₄→³F₄) increases, while the experimental lifetime of the Tm³⁺:³H₄ level decreases by increasing Tm₂O₃ concentration, which is attributed to the presence of a cross relaxation process. The most intensive emission at 1.8 μm is achieved from the germanate glass with the concentration of Tm₂O₃ reaches 1.0 wt%. The extended overlap integral method is used to calculate the microparameter of the energy transfer and the critical distance, which are derived to better understand the energy transfer process of thulium ions in the germanate glass responsible for emission at 1.8 μm.     

A high-resolution infrared study of the ν4 band of CH3I

The infrared spectrum of the ν₄ band of CH₃I around 3060 cm⁻¹ was studied at a resolution of 5.4 × 10⁻³ cm⁻¹. About 1850 transitions were assigned. The K range was from KΔK = −7 to KΔK = +9 and the highest J values were about 75. The anomalous rotational structures observed in the subbands ^PQ₆ and ^RQ₅ – ^RQ₇ were explained as a consequence of Coriolis and Fermi resonances with combination levels. The standard deviation of the least-squares fit with 19 parameters was 0.00083 cm⁻¹. In addition to the fundamental band, the hot band ν₃ + ν₄ − ν₃ was also studied.     

High-resolution Fourier transform study of the ν3 fundamental band of trans-formic acid

Using high-resolution Fourier transform spectra of trans-HCOOH recorded at 5.6 μm, we carried out an extensive analysis of the strong ν₃ fundamental band (carbonyl stretching mode) at 1776.83 cm^?1, starting from results of a previous analysis [Weber WH, Maker PD, Johns JWC, Weinberger E. J Mol Spectrosc 1987; 121: 243–60]. As pointed out in the literature, the ν₃ band is significantly perturbed by resonances due to numerous dark bands. We were able to assign series belonging to the ν₅+ν₇, ν₅+ν₉, ν₆+ν₇ and ν₆+ν₉ dark bands, located at 1843.48, 1792.63, 1737.96 and 1726.40 cm^?1, respectively. The model used to calculate energy levels accounts partly for the observed resonances, and enabled us to reproduce most of the observed line positions, within their experimental uncertainties. We also determined absolute line intensities with an accuracy estimated to 15%. Finally, we generated, for the first time, a list of line parameters for the 5.6 μm region of trans-formic acid.     

Spin splittings in the ν3 band of NO2

Spin splittings for several important atmospheric lines in the ν₃ band of NO₂ have been measured by diode laser. An improved spin-splitting program has been developed which takes into account the asymmetry effects in the lower K_a splittings. The measured spin splittings and the derived spin-rotational constants are reported in this study to a much higher accuracy than previously achieved.     

The high-resolution spectrum of the ν1 + ν2 band of NO2: A spin-induced perturbation in the ground state

The spectrum of the ν₁ + ν₂ band of NO₂ has been studied with a resolution of 0.025 cm⁻¹. Spin-rotation constants and rotational constants are reported. An interesting perturbation has been found in the ground state of the molecule which occurs when the K_a = 0 and K_a = 2 levels become accidentally nearly degenerate around N = 42. An explanation of this interaction is presented.     

Frequency stabilization of an InGaAsP DFB laser using a molecular absorption line at 1.54308 μm

Molecular absorption lines due to vibrational-rotational transitions in¹⁴NH₃ are observed near 1.5 m. An InGaAsP DFB laser is frequency stabilized to a linear absorption line within 500 MHz at 1543.08 nm. Such an absolute frequency-stabilized DFB laser is useful for coherent optical system applications owing to its long-term frequency stability and for residual gas detectors.     

High-resolution spectroscopy of difference and combination bands of SF6 to elucidate the ν3 + ν1 − ν1 and ν3 + ν2 − ν2 hot band structures in the ν3 region

The strong infrared absorption in the ν₃ S–F stretching region of sulphur hexafluoride (SF₆) near 948 cm^?1 makes it a powerful greenhouse gas. Although its present concentration in the atmosphere is very low, it is increasing rapidly, due to industrial pollution. The ground state population of this heavy species is only 32% at room temperature and thus many hot bands are present. Consequently, a reliable remote-sensing spectroscopic detection and monitoring of this species require an accurate modelling of these hot bands. We used two experimental set-ups at the SOLEIL French synchrotron facility to record some difference and combination bands of SF₆: (1) a new cryogenic multiple pass cell with 93 m optical path length and regulated at 163 ± 2 K temperature and (2) the Jet-AILES supersonic expansion set-up. With this, we could obtain high-resolution absorption spectra of the ν₃ ? ν₁, ν₃ ? ν₂, ν₁ + ν₃ and ν₂ + ν₃ bands at low temperature. These spectra could be assigned and analysed, thanks to the SPVIEW and XTDS computer programs developed in Dijon. We performed two global fits of effective Hamiltonian parameters. The first one is a global fit of the ground state, ν₂, ν₃, ν₃ ? ν₂, ν₂ + ν₃, 2ν₃ and 2ν₃ ? ν₃ rovibrational parameters, using the present spectra and previous infrared, Raman and two-photon absorption data. This allows a consistent refinement of the effective Hamiltonian parameters for all the implied vibrational levels and a new simulation of the 2ν₃ + ν₂ ? ν₂ hot band. The second global fit involves the present ν₃ ? ν₁ and ν₁ + ν₃ lines, together with previous ν₁ Raman data, in order to obtain refined ν₁ parameters and also ν₁ + ν₃ parameters in a consistent way. This allows to simulate the ν₃ + ν₁ ? ν₁ hot band.     

Measurements and calculations of H2-broadening and shift parameters of water vapour transitions of the ν1 + ν2 + ν3 band

The water vapour line broadening and shifting for 97 lines in the ν₁ + ν₂ + ν₃ band induced by hydrogen pressure are measured with Bruker IFS 125 HR FTIR spectrometer. The measurements were performed at room temperature, at the spectral resolution of 0.01 cm^?1 and in a wide pressure range of H₂. The calculations of the broadening γ and shift δ coefficients were performed in the semi-classical method framework with use of an effective vibrationally depended interaction potential. Two potential parameters were optimised to improve the quality of calculations. Good agreements with measured broadening coefficients were achieved. The comparison of calculated broadening coefficients γ with the previous measurements is discussed. The analytical expressions that reproduce these coefficients for rotational, ν₂, ν₁, and ν₃ vibrational bands are presented.     

A 13.3-W laser-diode-array end-pumped Nd:GdVO4 continuous-wave laser at 1.34 μm

We report a high-power laser-diode-array end-pumped 0.3 at.% Nd:GdVO₄ continuous-wave laser operating at 1.34 m. The maximum output power of 13.3 W was obtained at the incident pump power of 49.2 W, giving the corresponding optical conversion efficiency of 27% and the average slope efficiency of 28.5%. The thermal focal length of the Nd:GdVO₄ crystal under the pump power from 15.3 to 50 W was measured experimentally. PACS 42.55.Xi; 42.70.Hj     

Line intensities for the ν1, ν3 and ν1+ν3 bands of 34SO2

Using both high resolution (0.0018 cm^?1) and medium resolution (0.112 cm^?1) Fourier transform spectra of an enriched ³⁴S (95.3%) sample of sulfur dioxide, it has been possible to accurately measure a large number of individual line intensities for some of the strongest of the SO₂ bands, i.e. ν₁, ν₃ and ν₁₊ν₃. These intensities were least-squares fitted using a theoretical model which takes into account the vibration–rotation interactions linking the upper energy levels where needed, and, in this way, expansions of the various transition moment operators were determined. The Hamiltonian parameters determined in previous analyses together with these moments were then used to generate synthetic spectra for the bands studied and their corresponding hot bands providing one with an extensive picture of the absorption spectrum of ³⁴SO₂ in the spectral domains, 8.7, 7.4, and 4 μm.