Development of a stabilized low temperature infrared absorption cell for use in low temperature and collisional cooling experiments.

We have constructed a stabilized low temperature infrared absorption cell cooled by an open cycle refrigerator, which can run with liquid nitrogen from 250 to 80K or with liquid helium from 80K to a few kelvin. Several CO infrared spectra were recorded at low temperature using a tunable diode laser spectrometer. These spectra were analyzed taking into account the detailed effects of collisions on the line profile when the pressure increases. We also recorded spectra at very low pressure to accurately model the diode laser emission. Spectra of the R(2) line in the fundamental band of 13CO cooled by collisions with helium buffer gas at 10.5K and at pressures near 1 Torr have been recorded. The He-pressure broadening parameter (gamma(0) = 0.3 cm(-1) atm(-1)) has been derived from the simultaneous analysis of four spectra at different pressures.

Diode laser emission linewidth determination: application to H2O line profile studies in the 5 and 1.4 microm regions.

In order to study absorption line profiles using the stabilized diode laser spectrometer of Laboratoire de Physique Moléculaire et Applications (LPMA), a reliable determination of the emission line shape of different diodes laser is needed. In the near infrared region (1.39 and 1.66 microm) we used Distributed Feed Back diode lasers which operate around room temperature and in the middle infrared (5 and 8 microm) we used lead salt diode lasers cooled in a helium closed cycle cryostat or in a liquid nitrogen dewar. Some results obtained in H2O line profile studies in the 1.39 and 5 microm regions are presented as examples demonstrating how absorption line profile measurements can lead to erroneous values of the spectroscopic parameters when the contribution of the diode laser emission line width is neglected.

Torsional Splitting in the nu(5) Fundamental Infrared Band of CH(3)CD(3) and (13)CH(3)CD(3).

The nu(5) fundamental (C-C stretching) of CH(3)CD(3) shows a resolved torsional structure, caused by perturbations due mainly to the linear dependence of the torsional potential barrier on the normal coordinate Q(5). We were able to analyze this structure and to assign vibration-rotation transition wavenumbers for all five torsional components, classified according to the symmetry species of the G(18)((3)) extended molecular group. The torsional splitting pattern is qualitatively similar to that of a nondegenerate vibrational state with an even number of excited torsional quanta v(6). Explorative calculations show that the main perturber system should consist of the torsional components of the vibrational ground state correlating with v(6)=4 in the high barrier limit. The strength of the perturbation on the E(r0) torsional components of nu(5) increases rapidly with r, the E(40) component being the most affected. The observed transition wavenumbers can be reasonably fitted by a simplified model containing independent effective vibration-rotation parameters for the five different torsional components of nu(5), for both CH(3)CD(3) and (13)CH(3)CD(3). The trend of the determined values of the effective vibrational wavenumbers and rotational parameters over the torsional components supports the proposed vibration-torsion interaction mechanism, responsible for the observed torsional splittings. A strong anomaly observed in the rotational intensity distribution of nu(5) is discussed. Copyright 2001 Academic Press.

Absolute Intensities of the nu(1) and nu(3) Bands of (16)O(3).

New experimental data on the nu(1) and nu(3) bands of (16)O(3) improving the value of absolute line intensities have been obtained. The intensities of 295 lines have been measured with an average accuracy between 2.5% and 3% and the rotational expansion of the transition moment operators for the nu(1) and nu(3) bands has been deduced. Finally, a complete listing of line intensities has been computed with an intensity cutoff of 1x10(-25) cm(-1)/molecule cm(-2). Copyright 2001 Academic Press.

Line Intensities of (12)C(16)O(2) in the 1.2-1.4 µm Spectral Region.

The 7000-8500 cm(-1) spectral region of (12)C(16)O(2) has been investigated using the high-resolution FT spectrometer of LPPM in Orsay. The two strongest bands in this region are the 10031 <-- 00001 and 10032 <-- 00001 bands centered at 8294 and 8192 cm(-1). Line intensities in these two bands and in the 40013 <-- 00001 and 40014 <-- 00001 bands have been measured. Using the method of effective operators, these line intensities have been included in a new fit of effective dipole-moment parameters to all available experimental data in the same spectral region of (12)C(16)O(2). The corresponding calculated line intensities of the 10031 <-- 00001 and 10032 <-- 00001 bands are compared with the experimental ones. Copyright 2000 Academic Press.

Analysis of the Infrared Fourier Transform Spectrum of the Spectra of Silane in the Range 2930-3300 cm(-1).

The infrared spectrum of (28)SiH(4) between 2930 and 3300 cm(-1) was recorded using the Laboratoire de Physique Moléculaire et Applications (LPMA.) Fourier transform spectrometer. The instrumental response function width chosen makes it possible to obtain a Doppler-limited spectrum. The observed spectrum belongs to the tetrad built with one quantum of stretching mode (nu(1) or nu(3)) and one quantum of bending mode (nu(2) or nu(4)). The excited states are formed from eight vibrational sublevels: nu(1) + nu(2)(E), nu(1) + nu(4)(F(2)), nu(2) + nu(3)(F(1) + F(2)), and nu(3) + nu(4)(A(1) + E + F(1) + F(2)). The intricacy of the upper states was resolved using the variations of the line strength between the 297 K and 209 K spectra and the precise knowledge of the ground state. For analysis with the vibrational extrapolation method, we used the previous results for the fundamental bending dyad (nu(2)/nu(4)) and the stretching dyad (nu(1)/nu(3)). The Hamiltonian is expanded through the sixth order of approximation for the ground and the bending states, the fifth order for the stretching states, and the fourth order for the tetrad states in the Amat-Nielsen classification. About 1033 pieces of data are used in the analysis and the weighted standard deviation obtained is 4.6 x 10(-3) cm(-1). Copyright 1999 Academic Press.

The Water-Vapor nu(2) Band Lineshift Coefficients Induced by Nitrogen Pressure.

The water-vapor lineshift coefficients in the nu(2) band induced by nitrogen pressure were measured with a FT spectrometer of Paris University at the spectral resolution of 0.005 cm(-1) for the line with angular moment of upper states up to 16. Calculations were made using Anderson formulation of semiclassical impact theory. The calculated lineshifts agree satisfactorily with measured values, but for some lines, deviations were found. The analysis revealed the systematic J trend in subbranches, which consists of transitions with the same values of quantum number K(a) and equally changing K(a) and K(c). Copyright 1999 Academic Press.

Line Positions and Absolute Intensities in the Laser Bands of Carbon-12 Oxygen-17 Isotopic Species of Carbon Dioxide.

Infrared spectra of a carbon dioxide sample enriched with oxygen-17 have been recorded with a resolution of about 0.0025 cm-1 in the region of the laser bands near 10 and 9 µm, using the long path difference Fourier Transform Spectrometer of the LPMA in Paris. The two laser bands of the 16O12C17O and 17O12C18O species have been analyzed for the first time. Line intensities for several isotopic species have been measured in this region and the rotationless transition dipole moments and Herman-Wallis coefficients of the corresponding bands have been reported. In particular intensities, alternation in the spectra of 17O12C17O has been analyzed. Copyright 1999 Academic Press.

Infrared Fundamental and First Hot Bands of O12C17O Isotopic Variants of Carbon Dioxide.

Infrared spectra of 16O12C17O, 17O12C17O, and 17O12C18O in a carbon dioxide sample enriched with oxygen-17 have been recorded with a resolution of about 0.0025 cm-1 in the regions of the fundamental bands, nu2 (600-800 cm-1) and nu3 (2200-2400 cm-1), and in the region of the "forbidden" band, nu1 (1200-1400 cm-1), using the long path difference Fourier transform spectrometer of the LPMA in Paris. For each species, the first hot band in the 4.5-µm region and two hot bands at least in the 15-µm region have been studied for the first time, and a simultaneous reduction of wavenumbers measured in different spectral regions has been carried out yielding new or improved spectroscopic constants. Line intensities have been measured in the region of the nu2 and nu3 bands of 16O12C17O, and the corresponding rotationless transition dipole moments and Herman-Wallis coefficients have been reported. Copyright 1998 Academic Press.