Ab Initio Calculations and High-Resolution Spectroscopy of the Bending Pentad of SiH2D2 in the 10-16 µm Region.

The SiH2D2 asymmetric top has nine vibrational modes, five of them forming a pentad strongly perturbed by Coriolis interactions. High-level ab initio calculations of SiH2D2 have been performed which yield numerous spectroscopic parameters related to the harmonic and anharmonic force fields. The bending pentad comprising nu4(A1), nu7(B1), nu5(A2), nu9(B2), and nu3(A1) has been studied by high-resolution Fourier transform spectroscopy; the region 600-1050 cm-1 has been investigated with a resolution of ca. 4 x 10(-3) cm-1. Raman BOXCARS spectroscopy has been used for the infrared inactive nu5 band. The Raman apparatus function was 0.0054 cm-1. Assignments of about 4000 transitions including all bands have been made, mostly employing ground state combination differences techniques, and a global fit has been performed. The fundamentals nu4 (681.624 cm-1), nu7 (742.640 cm-1), nu5 (842.381 cm-1), nu9 (859.750 cm-1), and nu3 (942.741 cm-1) are strongly coupled by A-, B-, and C-type Coriolis interactions, and ab initio predictions of these interaction parameters were used to set up a network of interactions that was refined by the experimental data. The global standard deviation for the entire body of data is 7.1 x 10(-4) cm-1. Satisfactory synthetic spectra which are very sensitive to relative signs of dipole moment derivatives and Coriolis interaction constants were obtained with the guidance of ab initio calculations. Finally, fair to good agreement of experimental and ab initio calculated molecular parameters was obtained. For the first time, a complete analysis of the pentad of SiH2D2 in the 10-16 µm region has been carried out. A full set of rovibrational parameters is given for these five interacting levels, including first and second order Coriolis interaction constants. Copyright 1998 Academic Press.

Simultaneous Analysis of the 2nu2, nu1, and nu3 Bands of Hydrogen Telluride

Spectra of a natural sample of hydrogen telluride as well as a spectrum of monoisotopic H2 130Te have been recorded by means of Fourier transform spectrometry with a resolution of 0.003 cm-1 in the spectral domain 7.5-4.3 µm where it is easy to observe the main absorbing bands nu1 and nu3. We have located and assigned for the first time the 2nu2 band which appears in the lower wavenumber range of the recorded spectral domain near 1700 cm-1. It proved necessary to treat simultaneously the three states (020), (100), and (001). nu1 and nu3 are indeed Coriolis-coupled vibration-rotation bands and it was observed that a few rotational levels of (001) could not be fitted to within their experimental accuracy without considering the second-order Coriolis interaction between the rotational levels of (020) and (001). In this way all the experimental levels were calculated to within the experimental uncertainty, and precise sets of vibrational energies and rotational and coupling constants were obtained for the seven most abundant H2Te isotopic species, namely H2 130Te, H2 128Te, H2 126Te, H2 125Te, H2 124Te, H2 123Te, and H2 122Te. For the most abundant isotopic species H2 130Te the bands centers arenu0 (2nu2) = 1715.9568, nu0 (nu1) = 2065.2709, nu0 (nu3) = 2072.1101 cm-1. Copyright 1997Academic Press