Ab InitioCalculations and High-Resolution Spectroscopy of the Bending Pentad of SiH2D2in the 10–16 μm Region

✍ Scribed by M. Rotger; V. Boudon; B. Lavorel; S. Sommer; H. Bürger; J. Breidung; W. Thiel; M. Bétrencourt; J.-C. Deroche

• Publisher: Elsevier Science
• Year: 1998
• Tongue: English
• Weight: 422 KB
• Volume: 192
• Category: Article
• ISSN: 0022-2852
• DOI: 10.1006/jmsp.1998.7695

✦ Synopsis

The SiH 2 D 2 asymmetric top has nine vibrational modes, five of them forming a pentad strongly perturbed by Coriolis interactions. High-level ab initio calculations of SiH 2 D 2 have been performed which yield numerous spectroscopic parameters related to the harmonic and anharmonic force fields. The bending pentad comprising 4 ( A 1 ), 7 (B 1 ), 5 ( A 2 ), 9 (B 2 ), and 3 ( A 1 ) has been studied by high-resolution Fourier transform spectroscopy; the region 600 -1050 cm Ϫ1 has been investigated with a resolution of ca. 4 ϫ 10 Ϫ3 cm Ϫ1 . Raman BOXCARS spectroscopy has been used for the infrared inactive 5 band. The Raman apparatus function was 0.0054 cm Ϫ1 . 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 4 (681.624 cm Ϫ1 ), 7 (742.640 cm Ϫ1 ), 5 (842.381 cm Ϫ1 ), 9 (859.750 cm Ϫ1 ), and 3 (942.741 cm Ϫ1 ) 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 ϫ 10 Ϫ4 cm Ϫ1 . 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 SiH 2 D 2 in the 10 -16 m 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.