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The high resolution Fourier transform spectrum of the D20 (ν = ν1 + ν2/2 + ν3 = 3.5) polyad was analysed within the framework of the Hamiltonian model taking into account resonance interactions between the seven states (310), (211), (112), (013), (230), (131) and (032). Transitions belonging to the 2ν1 + ν2 + ν3, 3ν1 +ν2 and 3ν2 + 2ν3 bands were assigned in the experimentally recorded spectrum. This provided the possibility of obtaining spectroscopic parameters of the ‘visible’ states (211), (310) and (032) and of estimating the band centres, and the rotational and resonance interaction parameters of the ‘dark’ states (112) and (131).

The infrared spectra of PH3 molecule were recorded on a Bruker IFS 120HR Fourier transform spectrometer from 4000 to 9500 cm−1. The P–H stretching vibrational frequencies and intensities were derived from the experimental data. The Morse oscillator parameters De and α in the anharmonically coupled anharmonic oscillator local mode model were determined by the least-squares fitting with the observed vibrational band centers. The ab initio three-dimensional P–H stretching dipole moment surfaces were calculated by the density functional theory method. The dipole moment vectors were projected to three kinds of molecule-fixed reference systems. The corresponding dipole moment components were fitted to polynomial functions in terms of the P–H bond length displacements with the molecular symmetry taken into account. The absolute band intensities were obtained and then compared with the experimental data. The results showed that a proposed improved bond dipole model can predict the absolute band intensities within a factor of 2 for most of the observed transitions, indicating a reasonably good agreement.

Analysis of the high-resolution Fourier transform spectra of the D(2)O first decade was carried out in the framework of the Hamiltonian model which took into account resonance interactions between the seven states, (300), (201), (102), (003), (220), (121), and (022). Assigned from the experimentally recorded spectrum transitions belonged to the four bands, 2nu(1) + nu(3), 3nu(3), nu(1) + 2nu(2) + nu(3), and 3nu(1), gave the possibility both of obtaining rotational, centrifugal distortion, and resonance interaction parameters of "appeared" states, (201), (003), (121), and (300), and of estimating from the fit band centers, rotational, and resonance interaction parameters of the three "dark" states, (220), (022), and (102). Copyright 2000 Academic Press.

The solid neon matrix isolated spectrum of CO 2 are recorded in the 2–5 μm region. Natural and 13 C or 18 O enriched CO 2 samples were used and the nν 1 + ν 3 ( n = 0, 1, 2) series bands of different CO 2 isotopologues have been observed. The solid neon matrix shift due to Fermi-resonance of bands within the same vibrational polyad is analyzed.

The newly developed high resolution Fourier-transform intra-cavity laser absorption spectroscopy (FT-ICLAS) was utilized to record the νOD=5 stretching overtone of HOD at a resolution of 0.05 cm-1 in the region 12550–12900 cm-1. The spectrum was rotationally analysed and the spectroscopic parameters were derived from nonlinear least-squares fitting. Good agreement of the observed with the calculated energy levels was achieved.

The isotopic abundance of (85)Kr in the atmosphere, currently at the level of 10(-11), has increased by orders of magnitude since the dawn of nuclear age. With a half-life of 10.76 years, (85)Kr is of great interest as tracers for environmental samples such as air, groundwater and ice. Atom Trap Trace Analysis (ATTA) is an emerging method for the analysis of rare krypton isotopes at isotopic abundance levels as low as 10(-14) using krypton gas samples of a few micro-liters. Both the reliability and reproducibility of the method are examined in the present study by an inter-comparison among different instruments. The (85)Kr/Kr ratios of 12 samples, in the range of 10(-13) to 10(-10), are measured independently in three laboratories: a low-level counting laboratory in Bern, Switzerland, and two ATTA laboratories, one in Hefei, China, and another in Argonne, USA. The results are in agreement at the precision level of 5%.

Wepresentafully ab initiomodelandcalculationsofthespectralshapesofabsorptionlinesinapuremolecular gas under conditions where the influences of collisions and of the Doppler effect are significant. Predictions of the time dependence of dipole autocorrelation functions (DACFs) are made for pure CO2 at room temperature using requantized classical molecular dynamics simulations. These are carried, free of any adjusted parameter, on the basis of an accurate anisotropic intermolecular potential. The Fourier-Laplace transforms of these DACFs then yield calculated spectra which are analyzed, as some measured ones, through fits using Voigt line profiles. Comparisonsbetweentheoryandvariousexperimentsnotonlyshowthatthemainline-shapeparameters(Lorentz pressure-broadening coefficients) are accurately predicted, but that subtle observed non-Voigt features are also quantitatively reproduced by the model. These successes open renewed perspectives for the understanding of the mechanisms involved (translational-velocity and rotational-state changes and their dependences on the molecular speed) and the quantification of their respective contributions. The proposed model should also be of great help for the test of widely used empirical line-shape models and, if needed, the construction of more physically based ones.

The low-lying electronic states of Yb isolated in a solid Ne matrix are characterized through absorption and emission spectroscopy. The absorption spectra of matrix isolated Yb while pumped into its triplet states have been recorded for the first time and the 6s6p (3)P(J) → 5d6s (3)D(1, 2) transition frequencies obtained. Under matrix conditions, the structure of these states is found to be qualitatively the same as in the free atom, but the intersystem crossing rate is observed to be several orders of magnitude greater. A proposed explanation for this is curve crossings between the bound potential energy surface correlated to the 6s6p (1)P(1) state and the potential energy surfaces correlated to the 5d6s (3)D(1, 2) states in isolation. The potentials of the Yb·Ne dimer in its lowest electronic states are computed ab initio and used in a pairwise cluster model to explicitly demonstrate these curve crossings.

International audience; The very weak S(0)-S(3) electric quadrupole transitions of the second overtone band of molecular hydrogen have been recorded in the laboratory by continuous-wave cavity ring-down spectroscopy near 0.8 μm. The ultrahigh sensitivity of the spectrometer (αmin ~ 1 × 10-10 cm-1) allows us to detect the considered transitions at a relatively low sample pressure (50-750 torr). The line positions, intensity, and pressure-shift coefficients are derived from a fit of the line shape using a Galatry profile. Compared with literature values, the relative differences between the experimental and theoretical transition intensities are reduced by one order of magnitude, reaching a value of about 2% mainly dependent of the line-shape function adopted for the profile fitting. The thermal equilibrium relative intensity of the S(1) to S(0) line is determined with an accuracy of 0.4%, which can be used to probe the ortho- to para-H2 concentration ratio. Our measurements confirm the quality of the high-level ab initio calculations, including the relativistic and quantum electrodynamics corrections.

A continuous-wave cavity ring-down spectrometer with sub-MHz precision has been built using the sideband of a frequency stabilized laser as the tunable light source. The sideband is produced by passing the carrier laser beam through an electro-optic modulator (EOM) and then selected by a short etalon on resonance. The carrier laser frequency is locked to a longitude mode of a thermo-stabilized Fabry-Perot interferometer (FPI) with a long-term absolute frequency stability of 0.2 MHz (5 × 10(-10)). Broad and precise spectral scanning is accomplished, respectively, by selecting a different longitudinal mode of the FPI and by tuning the radio-frequency driving the EOM. The air broadened water absorption line at 12,321 cm(-1) was studied to test the performance of the spectrometer.

The Boltzmann constant can be optically determined by measuring the Doppler width of an absorption line of molecules at gas phase. We propose to apply a near infrared cavity ring-down (CRD) spectrometer for this purpose. The superior sensitivity of CRD spectroscopy and the good performance of the near-ir lasers can provide ppm (part-per-million) accuracy which will be competitive to present most accurate result obtained from the speed of sound in argon measurement. The possible influence to the uncertainty of the determined Doppler width from different causes are investigated, which includes the signal-to-noise level, laser frequency stability, detecting nonlinearity, and pressure broadening effect. The analysis shows that the CRD spectroscopy has some remarkable advantages over the direct absorption method proposed before. The design of the experimental setup is presented and the measurement of C2H2 line near 0.8 μm at room temperature has been carried out as a test of the instrument.

A cavity ring-down spectrometer was built up using a CW tunable Ti: sapphire laser. The experiments show that not only the spectral resolution is up to the 10(-4) cm(-1) level, but the detecting sensitivity also exceeds 10(-10) cm(-1). With the measurements of the absorption spectroscopy of C2H2 near 12,696.4 cm(-1), the quantitative capability of the instrument was demonstrated. Through the spectroscopy of the samples mixed with trace C2H2 in N2 gas, the detection limit of C2H2 was determined to be 0.2 ppm.

Neutral ytterbium atoms embedded in solid neon qualitatively retain the structure of free atoms. Despite the atom-solid interaction, the 6s6p {sup 3}P{sub 0} level is found to remain metastable with its lifetimes determined to be in the range of ten to hundreds of seconds. The atomic population can be almost completely transferred between the ground level and the metastable level via optical excitation and spontaneous decay. The dynamics of this process is examined and is used to explicitly demonstrate that the transition broadening mechanism is homogeneous.

The empirical line parameters of over 12,000 methane transitions have been obtained at 80 K in the 1.58 μm transparency window (6165–6750 cm −1 ) which is of importance for planetary applications. This line list (WKC-80K) was constructed from high sensitivity spectra of normal abundance methane recorded by CW-Cavity Ring Down Spectroscopy at low temperature. The minimum intensity reported is on the order of 5×10 −30 cm/molecule. High resolution Fourier transform spectra have also been recorded using enriched CH 3 D samples at 90–120 K in order to facilitate identification of monodeuterated methane features in the methane line list at 80 K. The CH 3 D relative contribution in the considered region is observed to be much larger at 80 K than at room temperature. In particular, CH 3 D is found dominant in a narrow spectral window near 6300 cm −1 corresponding to the highest transparency region. Using a similar line list constructed at room temperature (Campargue A, Wang L, Liu AW, Hu SM and Kassi S. Empirical line parameters of methane in the 1.63–1.48 μm transparency window by high sensitivity Cavity Ring Down Spectroscopy. Chem Phys 2010;373:203–10.), the low energy values of the transitions observed both at 80 K and at room temperature were derived from the variation of their line intensities. Empirical lower states and J -values have been obtained for 5671 CH 4 and 1572 CH 3 D transitions representing the most part of the absorbance in the region. The good quality of these derived energy values is demonstrated by the marked propensity of the corresponding CH 4 lower state J values to be close to integers. The WKC line lists at 80 K and room temperature provided as Supplementary Material allow one accounting for the temperature dependence of methane absorption between these two temperatures. The importance of the 80 K line list for the study of Titan and other methane containing planetary atmospheres is underlined and further improvements are proposed. The resulting information will advance the theoretical modeling of the methane spectrum in the 1.58 μm transparency window.

Atom trap trace analysis, a laser-based atom counting method, has been applied to analyze atmospheric $^{39}\mathrm{Ar}$ ($\mathrm{\text{half-life}}=269\text{ }\text{ }\mathrm{yr}$), a cosmogenic isotope with an isotopic abundance of $8\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}16}$. In addition to the superior selectivity demonstrated in this work, the counting rate and efficiency of atom trap trace analysis have been improved by 2 orders of magnitude over prior results. The significant applications of this new analytical capability lie in radioisotope dating of ice and water samples and in the development of dark matter detectors.

The high resolution absorption spectrum of methane in the 1.58 μm transparency window has been recorded at room temperature and at 79 K by CW-Cavity Ring Down Spectroscopy using a cryogenic cell and a series of Distributed Feed Back (DFB) diode lasers. The achieved sensitivity ( α min ∼ 3 × 10 −10 cm −1 ) has allowed for a detailed characterization of the 6289–6526 cm −1 region which corresponds to the lowest opacity of the transparency window. A list of 6868 and 4555 transitions with intensities as weak as 1 × 10 −29 cm/molecule was constructed from the recordings at 297 and 79 K, respectively. By comparison with a spectrum of CH 3 D recorded separately by Fourier Transform Spectroscopy, 1282 and 640 transitions of monodeuterated methane, CH 3 D, in natural abundance in our sample were identified at 297 and 79 K, respectively. The rotational temperature determined from the intensity distribution of the 3 ν 2 band of CH 3 D (79.3 K) was found in good agreement with the temperature value previously obtained from the Doppler line broadening. The reduction of the rotational congestion by cooling down to 79 K reveals a spectral region near 6300 cm −1 where CH 3 D transitions are dominant. The low energy values of the transitions observed both at 79 K and at room temperature were derived from the variation of their line intensities. These transitions with lower energy determination represent 93.9% and 68.4% of the total absorbance in the region, at 79 K and room temperature, respectively. The quality of the obtained empirical low energy values is demonstrated for CH 4 by the marked propensity of the empirical low J values to be close to integers. The line lists at 79 K and room temperature provided as Supplementary Material allow accounting for the temperature dependence of methane absorption between these two temperatures. The investigated region covering the 5 ν 4 band of the 12 CH 4 isotopologue will be valuable for the theoretical treatment of this band which is the lowest energy band of the icosad.

A midinfrared laser spectrometer is built up based on the difference frequency generation (DFG) of a Nd:YAG (yttrium aluminum garnet) laser and a tunable Ti:sapphire (Ti:Sa) laser. Tuning the Ti:Sa laser and operating properly with the periodically poled lithium niobate crystal, the DFG emission is tunable in the spectral range of 2.3-5.0 microm. The 1064 nm Nd:YAG laser frequency is stabilized to the 10(-6) cm(-1) level on a Doppler-broadened I(2) absorption line at 532 nm. As a result, the DFG emission frequency is stabilized within 1x10(-4) cm(-1). The measurement of an absorption line of CH(4) near 3 mum demonstrates that the DFG spectrometer is very suitable for the molecular absorption line profile studies in the midinfrared region.

Observations of the jet-cooled infrared spectrum of CH(3)O in the CH stretching region have been extended, down to 2756 cm(-1) and up to 3003 cm(-1). In the lower frequency extension, a single vibronic band has been assigned. In the higher frequency region, the spectrum becomes complex above 2900 cm(-1) and remains so until near 2970 cm(-1) where it rapidly becomes sparse. Including the single vibronic band previously reported, a total of four bands have been assigned. Two bands including the original one follow a perpendicular DeltaP = +1 rotational selection rule and the other two bands follow a parallel DeltaP = 0 selection rule. In addition to these in the congested region between 2900 and 2970 cm(-1), ten isolated sub-bands (two P'' = -1/2, two P'' = +1/2, and six P'' = +1.5) have been assigned, but it has so far not been possible to connect these together to form bands. Taken together these observations suggest that there are strong vibronic couplings between the two CH stretching vibrations and the overtone and combination levels in the region.

The Boltzmann constant kB is a fundamental physical constant in thermodynamics. The present CODATA recommended value of kB is 1.3806488(13) × 10–23 J/K (relative uncertainty 0.91 ppm), which is mainly determined by acoustic methods. Doppler broadening thermometry (DBT) is an optical method which determines kB T by measuring the Doppler width of an atomic or molecular transition. The methodology and problems in DBT are reviewed, and DBT measurement using the sensitive cavity ring-down spectroscopy (CRDS) is proposed. Preliminary measurements indicate that CRDS-based DBT measurement can potentially reach an accuracy at the 1 ppm level.

Fourier transform spectra of water vapor enriched in 18O and 17O were recorded between 8012 and 9336 cm−1 and analyzed for the first time. High accuracy ab initio predictions of line positions and intensities by Partridge and Schwenke [J. Chem. Phys. 106 (1997) 4618–4639; 113 (2000) 6592–6597] were used in the process of spectrum assignment. Transitions involving the (031), (111), (130), (210), and (012) upper vibrational states were identified in the recorded spectra. As a result, 514 and 244 precise ro-vibrational energy levels were derived for the H218O and H217O molecules, respectively. High-order resonance perturbations between levels of the vibrational states involved were evidenced leading to the identification of a number of rotational levels of the (050) and (060) highly excited bending states.

The data of line intensities of the fundamental and low overtone absorption bands of phosphine are the basic reference data for the applications in quantative analysis and astronomy. The method of high-resolution Fourier-transform spectroscopy study on the absorption line intensities is discussed. With a series of measurement and fitting the line profiles, altogether 1760 absorption lines intensities of phosphine were obtained, corresponding to five bands in the 1950-2480 cm(-1) region and four bands in the 3 280-3 580 cm(-1) region. The accuracy of the line intensities was estimated to be +/-6%.

Extensive rovibrational line lists were computed for nine isotopologues of the CO molecule, namely, {sup 12}C{sup 16}O, {sup 12}C{sup 17}O, {sup 12}C{sup 18}O, {sup 13}C{sup 16}O, {sup 13}C{sup 17}O, {sup 13}C{sup 18}O, {sup 14}C{sup 16}O, {sup 14}C{sup 17}O, and {sup 14}C{sup 18}O in the ground electronic state with v ≤ 41, Δv ≤ 11, and J ≤ 150. The line intensity and position calculations were carried out using a newly determined piece-wise dipole moment function (DMF) in conjunction with the wavefunctions calculated from an experimentally determined potential energy function from Coxon and Hajigeorgiou. A direct-fit method that simultaneously fits all the reliable experimental rovibrational matrix elements has been used to construct the dipole moment function near equilibrium internuclear distance. In order to extend the amount and quality of input experimental parameters, new Cavity Ring Down Spectroscopy experiments were carried out to enable measurements of the lines in the 4-0 band with low uncertainty as well as the first measurements of lines in the 6-0 band. A new high-level ab initio DMF, derived from a finite field approach has been calculated to cover internuclear distances far from equilibrium. Accurate partition sums have been derived for temperatures up to 9000 K. In additionmore » to air- and self-induced broadening and shift parameters, those induced by CO{sub 2} and H{sub 2} are now provided for planetary applications. A complete set of broadening and shift parameters was calculated based on sophisticated extrapolation of high-quality measured data. The line lists, which follow HITRAN formalism, are provided as supplementary material.« less

International audience; The high-resolution (0.005 cm−1) Fourier transform infrared spectrum of PH3 is recorded and analyzed in the region of the fundamental stretching bands, ν1 and ν3. The ν2 + ν4 and 2ν4 bands are taken into account also. Experimental transitions are assigned to the ν1, ν3, ν2 + ν4, and 2ν4 bands with the maximum value of quantum number J equal to 15, 15, 13, and 15, respectively. a1–a2 splittings are observed and described up to the value of quantum number K equal to 10. The analysis of a1/a2 splittings is fulfilled with a Hamiltonian model which takes into account numerous resonance interactions among all the upper vibrational states

The high-resolution Fourier transform spectrum of the D(2)O molecule was recorded in the 3200-4200 cm(-1) region, where the bands of the second triad of interacting vibrational states are located. As a result of the theoretical analysis, both the rotational-vibrational structure of the (011) vibrational state was improved, and the rotational energies of the (110) and (030) vibrational states were determined for the first time up to rotational quantum numbers J(max.) = 15 and 14, respectively. Copyright 2000 Academic Press.

The high-resolution Fourier transform spectra of the D(2)O molecule have been recorded and assigned in the 4200-5700 cm(-1) region where the vibration-rotation bands 2nu(1), 2nu(3), nu(1) + nu(3), nu(1) + 2nu(2), 2nu(2) + nu(3), and 4nu(2) are located. The presence of numerous and very strong accidental perturbations between the states of the hexad makes it necessary to take into account not only ordinary resonance interactions of the Fermi, Darling-Dennison, and/or Coriolis types, but interactions between the states (v(1)v(2)v(3)) and (v(1) -/+ 2v(2) +/- 2v(3) +/- 1) as well. Parameters of all six vibrational states of the hexad were obtained from the fit of experimental energy values. Copyright 2000 Academic Press.

A high resolution and high sensitivity spectroscopic technique is developed by utilizing a Bruker IFS 120HR Fourier-transform spectrometer to detect the absorption spectra of samples inside a Ti:Sapphire laser cavity. A trigger-sampling system makes it possible to investigate the evolution of intra-cavity laser absorption spectra with the generation time. Owing to the multiplex advantage of FTS, the quantum noise in ICLAS can be significantly reduced in FT-ICLAS. The absorption of atmospheric water vapor in the range of 12450 - 12700 cm -1 was recorded at a resolution of 0.05 cm -1 to examine the performance of our FT-ICLAS apparatus. With 200 scans on the FT-ICLAS within 2 hours, a sensitivity of 10 -9 cm -1 was obtained. It is also demonstrated that the FT-ICLAS is able to record both positions and intensities in a wide spectral range. This technique was applied to measure the HOD v OD equals 5 overtone in the range of 12550 - 12900 cm -1 with a resolution of 0.05 cm -1 . The spectrum was analyzed with the ground states combination differences method and the spectroscopic parameters were obtained. For 81.1% rotational levels in this band, the difference between calculate and experimental energy was less than 0.01 cm -1 which indicated that both the recording and analyzing of this spectrum were successful.

The 782 nm band of CO{sub 2}, in a transparent window of Earth's atmosphere, was the first CO{sub 2} band observed 80 yr ago in the spectra of Venus. The band is very weak and therefore not saturated by the thick atmosphere of Venus, but its spectral parameters are still very limited due to the difficulty of detecting it in the laboratory. It is the highest overtone (ν{sub 1} + 5ν{sub 3}) of CO{sub 2} given in widely used spectroscopy databases such as HITRAN and GEISA. In the present work, the band is studied using a cavity ring-down spectrometer with ultra-high sensitivity as well as high precision. The positions of 55 lines in the band were determined with an absolute accuracy of 3 × 10{sup –5} cm{sup –1}, two orders of magnitude better than previous studies. The line intensities, self-induced pressure broadening coefficients, and the shift coefficients were also derived from the recorded spectra. The obtained spectral parameters can be applied to model the spectra of the CO{sub 2}-rich atmospheres of planets like Venus and Mars.

The infrared absorption spectra of the H2O, HDO, and D2O monomers isolated in solid N2 have been recorded at various temperatures between 4 and 30 K. A study of the absorption features of the ν1, ν2, and ν3 vibrational modes for each monomer shows their optical line shapes to be strongly temperature dependent. For all three modes, a decrease in the absorption amplitude and a proportional broadening of the linewidth was observed with increasing temperature, while the integrated absorbance remained constant. These observations were explained in terms of phonon coupling, by which high frequency intramolecular modes decay by exciting matrix phonons. Fits of the linewidth for the lowest frequency ν2 vibrational mode to the predicted vibrational relaxation rate in a solid medium gave average phonon mode frequencies consistent with the Debye frequency for solid N2.

The third CH stretching vibration overtone (4ν(CH)) of the acetylene molecule has been a prototype for intra-molecular dynamics studies. Using a sensitive cavity ring-down spectrometer calibrated with precise atomic transitions, the absolute line frequencies of 50 lines of this band have been determined with sub-MHz accuracy, or relatively 2 × 10(-9). The accuracy is also confirmed by the combination differences between the transitions sharing the same upper level. The improved accuracy, two orders of magnitude better than previous studies, allows us to reveal finer ro-vibrational couplings. Fitting of the rotational energies indicates that the J-dependent interactions take place after J7. The precise line positions present useful confinements to the models of the intra-molecular interactions of the acetylene molecule.

The single atom counting rate of a rare isotope and the loading rate of another stable isotope with an abundance over 10 orders of magnitude larger are measured in one atom trap. The linear correlation between the measured counting/loading rates is examined to determine the (84)Kr/(82)Kr and (85)Kr/(83)Kr ratios of a Kr gas sample. Experiments show that the relative uncertainty is reduced to 1.3% when the single atom counting rate of (85)Kr is normalized by the measured (83)Kr loading rate. The measurement of the normalized single atom counting rate can be used to determine extremely low (10(-16)-10(-11)) isotope abundance. This normalization method is robust and can also be applied in other atomic systems.

A continuous-wave cavity ring-down spectrometer has been built for precise determination of absolute frequencies of Doppler-broadened absorption lines. Using a thermo-stabilized Fabry-Pérot interferometer and Rb frequency references at the 780 nm and 795 nm, 0.1 - 0.6 MHz absolute frequency accuracy has been achieved in the 775-800 nm region. A water absorption line at 12579 cm(-1) is studied to test the performance of the spectrometer. The line position at zero-pressure limit is determined with an uncertainty of 0.3 MHz (relative accuracy of 0.8 × 10(-9)).

A microwave-driven discharge is used to produce a thermal beam of metastable krypton atoms at the 5s[3∕2]2 level with an angular flux density of 7×1014s−1sr−1, while consuming 1×1017kryptonatoms∕s. This source of atomic beam uses commercially available microwave parts, and has achieved comparable beam flux and excitation efficiency with a previously described source that employs a rf-driven discharge [C. Y. Chen et al., Rev. Sci. Instrum. 72, 271 (2001)].

The vibrational spectra of SiH2Cl2 have been recorded in the 1000-13,000 cm(-1) region, utilizing the Fourier-transform spectroscopy and Fourier-transform intracavity laser absorption spectroscopy. Totally 61 band centers and intensities are derived from the infrared spectra. An ab initio quartic force field is obtained by applying the second-order Moller-Plesset perturbation theory and correlation-consistent polarized valence triplet-zeta basis sets [J. Chem. Phys. 90, 1007 (1989); 98, 1358 (1993)]. Most observed bands are assigned by the vibration analysis based on the second-order perturbation theory. Reduced-dimensional ab initio dipole moment functions (two dimensional and three dimensional) have also been calculated to investigate the absolute band intensities of the SiH2 chromophore. The calculated values agree reasonably with the observed ones.

High-quality broadband infrared high-resolution spectra were obtained by use of the intracavity laser absorption spectroscopy technique with a Ti:sapphire laser in combination with a continuous-scan Fourier-transform (FT) interferometer. With electronic filtering used to smooth out the fluctuations of the laser power, the absorption of atmospheric water vapor in the range of 12,450-12,700 cm(-1) was recorded at a resolution of 0.05 cm(-1). A signal-to-noise ratio of greater than 300 was observed in this spectrum, corresponding to a minimum detectable absorption of approximately 2 x 10(-9) cm(-1). Comparison with previous measurements by use of a conventional FT technique shows that this method gives absorption spectra with highly accurate line positions along with reasonable line intensities. Investigation of the evolution of intracavity laser absorption spectra with the generation time is also shown to be possible with a continuous-scan FT spectrometer by use of the interleave rapid-scan method.

The HDO absorption FT spectrum is recorded and analyzed in the 7500–8200 cm−1 spectral region. The high accuracy ab initio calculation of Schwenke and Partridge was successfully applied for spectrum assignment that resulted in derivation of 508 precise rovibrational energy levels for the (3 0 0), (0 3 1), (1 1 1), (0 6 0), (2 2 0), and (0 0 2) states, with 295 of them being reported for the first time. In particular, eight new energy levels, including the band center at 7914.3170 cm−1, were derived for the highly excited bending (0 6 0) state from transitions borrowing their intensities through local high-order resonance coupling with the (3 0 0) and (0 3 1) states.