The v2 = 1, 2 and v4 = 1 bending states of 15NH3 and their analysis at experimental accuracy.

15NH3 is the object of extensive investigation due to the central role of ammonia in astronomical sciences and to the complexity of modeling its interacting vibrationally excited states. Of major interest in astrochemistry is the determination of the 14N/15N ratio in space, characterized by unexpected variability among different solar system objects and reservoirs. Recently, the spectroscopic analysis of ground and v2 = 1 a, s states of 15NH3 has been completed at experimental accuracy. Here, the characterization of the a, s inversion symmetry levels of v2 = 1, 2 and v4 = 1 states is presented. New spectra of 15NH3 have been recorded from 325 to 2000 cm-1 at a resolution ranging from 0.00096 cm-1 to 0.003 cm-1, using the Canadian Light Source synchrotron at CLS. 7518 transitions covering nine bands, ν2, 2ν2, ν4, 2ν2 ← ν2, ν4 ← ν2, 2ν2 ↔ ν4 and the inversion-rotation transitions in the excited states, have been fitted simultaneously. The effective Hamiltonian adopted includes all symmetry allowed interactions between and within the studied excited states, according to the most recent results on ammonia. The transitions have been reproduced at experimental accuracy using 185 spectroscopic parameters, determined with high precision. The leading diagonal parameters, Gv, B, C, D's, compare well with those of 14NH3. The wavenumbers of the assigned transitions are compared with their theoretically predicted values. An improved set of ground state parameters is also derived. These results noticeably improve the wavenumber line list in the high-resolution transmission molecular absorption (HITRAN) database.

Doppler broadening thermometry of acetylene and accurate measurement of the Boltzmann constant.

In this paper, we present accurate measurements of the fundamental Boltzmann constant based on a line-shape analysis of acetylene spectra in the ν1 + ν3 band recorded using a tunable diode laser. Experimental spectra recorded at low pressures (0.25 - 9 Torr), have been analyzed using a Speed Dependent Voigt model that takes into account the molecular speed dependence effects. This line-shape model reproduces the experimental data with good accuracy and allows us to determine precise line-shape parameters for the P(25) transition of the ν1 + ν3 band. From the recorded spectra we obtained the Doppler-width and then determined the Boltzmann constant, k(B).

Broadening and line mixing in the 20 (0)0<--01 (1)0, 11 (1)0<--00 (0)0 and 12 (2)0<--01 (1)0 Q branches of carbon dioxide: experimental results and energy-corrected sudden modeling.

Using both a difference frequency spectrometer and a Fourier transform spectrometer, we have measured transitions in the 12 (2)0<--01 (1)0 band of carbon dioxide at room temperature and pressures up to 19 atm. The low-pressure spectra were analyzed using a variety of standard spectral profiles, all with an asymmetric component to account for weak line mixing. For this band, we have been able to retrieve experimental line strengths and the broadening and weak mixing parameters. In this paper we also compare the suitability of the energy-corrected sudden model to predict mixing in the two previously measured Q branches 20 (0)0<--01 (1)0, the 11 (1)0<--00 (0)0, and the present Q branch of pure CO(2), all at room temperature.

Lineshifts in the Fundamental Band of CO: Confirmation of Experimental Results for N(2) and Comparison with Theory.

We have used a three-channel version of a tunable difference frequency laser spectrometer to measure the collisionally induced lineshifts at room temperature for 26 lines of the fundamental band of CO perturbed by nitrogen. Each lineshift was obtained directly by comparing the line center positions of two simultaneous recordings, one for a pressure-shifted line, and the other for the same line in pure CO line at very low pressure. The experimental results are found to be in complete agreement with earlier measurements and confirm that shifts as small as 3 MHz may be measured in such a system. Our results are compared with theoretical calculations. The part of the shifting coefficient antisymmetric with respect to a change in sign of the line number m, is in disagreement with the calculations. Copyright 1999 Academic Press.

Line Broadening and the Temperature Exponent of the Fundamental Band in CO-N(2) Mixtures.

We have measured the width, Gamma, of many P and R lines of the fundamental vibration-rotation band of CO perturbed by N(2) at 348 K and pressures of about 50 kPa. We have also extended the measurements made earlier at room temperature. The broadening coefficients, gamma = Gamma/pressure, were obtained with an accuracy of 0.3% by fitting with a Lorentzian, a Voigt, and an empirical lineshape model that blends together a hard-collision model and a speed-dependent Lorentzian profile. In all cases the results are represented by an empirical exponential power law polynomial in the line number, m. Combining the data at the two temperatures yields the exponent n in the scaling law gamma(T(1))/gamma(T(2)) = (T(1)/T(2))(-n), as a function of line number. The broadening coefficients and the variation of the temperature exponent line number are compared with theory. In addition, the line-mixing parameters are also reported at 348 and 301 K. Copyright 1999 Academic Press.

Fourier Transform Infrared Spectroscopy and Vibrational Coupling in the OH-Bending Band of 13CH3OH.

We present in this work a high-resolution Fourier transform infrared study of the OH-bending vibrational band of 13CH3OH. We have investigated the 1070-1400 cm-1 spectral region at 0.002 cm-1 resolution using the modified Bomem DA3.002 Fourier transform spectrometer at the Steacie Institute for Molecular Sciences at the National Research Council of Canada in Ottawa. This study has led to (i) determination of excited-state J(J + 1) subband expansion coefficients and (ii) characterization of a variety of interactions coupling the different vibrational modes, notably a strong Fermi resonance between the OH bend and the torsionally excited CH3-rocking mode. The OH-bending band is widely spread with Q subbranches grouped in two peaks at about 1312 and 1338 cm-1. The lower levels for all assigned subbands were confirmed using closed loops of IR and FIR transitions. The subbands have been fitted to J(J + 1) power-series expansions in order to obtain the subband origins and the state-specific energy expansion coefficients for both the OH-bending and excited torsional CH3-rocking states. The strong interaction between the OH-bending state and the first excited torsional CH3-rocking state gives rise to several "extra" forbidden subbands due to intensity borrowing. The asymmetry splitting of the (ntauK) v = (122)OH A OH-bending doublet was found to be anomalously small, and the splitting of the (122)rA CH3-rocking doublet is observed to be enhanced. We have identified a network of intermode interactions causing this unusual behavior, but a quantitative analysis of the vibrational coupling is restricted by limited knowledge of the unperturbed positions of the interacting levels. All these interactions provide relaxation channels for intramolecular vibrational redistribution among the lower vibrational modes in 13CH3OH. Another important finding is that the torsion-K-rotation energy curves in the OH-bending state display an inverted pattern compared to the ground state. Copyright 1998 Academic Press.

Fourier Transform Infrared Spectroscopy of the First CO-Stretch Overtone Band of 13CH3OH.

This paper presents a high-resolution Fourier transform infrared study of the first CO-stretch overtone band of 13CH3OH. The spectrum has been recorded at the Justus-Liebig University, Gießsen, Germany on their Bruker IFS 120 HR Fourier transform spectrometer. We have assigned parallel subbands in the torsional state n = 0 for K values up to 6. Each individual subband has been fitted to a J(J + 1) power series expansion in order to obtain the subband origin and the state-specific energy expansion coefficients for the first CO-stretch overtone state. The average rotational constant B in the CO-stretch vCO = 2 state was found to be 0.768 cm-1, forming a smooth series with that of 0.777 cm-1 obtained in the vCO = 1 state and the ground state value of 0.787 cm-1. Modeling of the excited state torsion-vibration energy level structure derived from the subband origins is then discussed and molecular parameters in the vCO = 2 state are proposed. The value obtained for the barrier height to internal rotation is 377.06 +/- 0.52 cm-1, nearly indistinguishable from the value 378.65 cm-1 reported for the CO-stretch vCO = 1 state. The vibrational energy is found to be 2020.9 +/- 1.4 cm-1. The harmonic wavenumber for the CO-stretch vibration in 13CH3OH was calculated to be omega = 1029.9 cm-1. The anharmonicity constant of this vibration is omegax = 6.5 cm-1, giving x = 6.3 x 10(-3). We have also observed asymmetry-induced K doubling for the subbands of A symmetry for K values from 1 to 3 at sufficiently high J values. The size of the splitting coefficients is similar to those observed for the CO-stretch fundamental, with the exception of those for the K = 3A doublet, where the observed splitting is about 18% larger than that for the ground and CO-stretch vCO = 1 states. Copyright 1998 Academic Press.

New Measurements and Assignments in the Millimeter-Wave Spectrum of CD3OH

The ground state rotational spectrum of CD3OH has been revisited in the millimeter-wave range. A total of 216 transition frequencies have been measured and assigned in the 117-179 GHz spectral range, including about 40 transitions previously reported. The spectrum was recorded at the Justus-Liebig University in Giessen, Germany using a frequency modulated millimeter-wave spectrometer. The assignments for the CD3OH transitions were predicted based on energy levels calculated using preliminary results of the global fit of microwave, millimeter-wave, and far-infrared data of Walsh et al. (Paper FC04 presented at the 52nd International Symposium of Molecular Spectroscopy, Columbus, OH, 1997). The new measurements have substantially enlarged the accurate millimeter-wave component of the data set available for the global fit and have allowed Walsh et al. to obtain significant improvement in the CD3OH molecular parameters (J. Mol. Spectrosc. 188, 85-93, 1998). The low residuals between observed and calculated frequencies highlight the quality of the global fit results. Copyright 1998 Academic Press.

New High-Resolution Analysis of the nu3, nu4, and nu6 Bands of D2CO Measured by Fourier Transform Spectroscopy

A reanalysis of the nu3, nu4, and nu6 interacting bands of D2CO has been carried out in the region 850-1250 cm-1 using high-resolution Fourier transform spectra recorded at Giessen. As compared to the previous study of these bands (1987, K. Nakagawa, R. H. Schwendeman, and J. W. C. Johns, J. Mol. Spectrosc. 122, 462-476) higher J and Ka transitions were assigned for the three bands, leading to a better determination of the upper state constants. The v3 = 1, v4 = 1, and v6 = 1 experimental energy levels were introduced in a least-squares fit calculation together with the microwave measurements available in the literature in order to obtain the upper state parameters (band centers, rotational and coupling constants). In this calculation, which allowed us to reproduce both the infrared and the microwave measurements to within their experimental accuracies, the A-, B-, and C-type Coriolis interactions involving the rotational levels belonging to the v4 = 1 and v6 = 1, v3 = 1 and v4 = 1, and v3 = 1 and v6 = 1 interacting states respectively were explicitly taken into account. Finally, from the intensities, a new determination of the relative values of the q3, q4, and q6 first derivatives of the D2CO dipole moment was performed. Copyright 1998 Academic Press. Copyright 1998Academic Press