The Si–H stretching–bending overtone polyads of SiHF3: Assignments, band 
intensities, internal coordinate force field, and ab initio dipole moment 
surfaces

Lin, Hai; Bürger, Hans; Mkadmi, El Bachir; He, Sheng-Gui; Yuan, Lan-Feng; Breidung, Jürgen; Thiel, Walter; Huet, Thérèse R.; Demaison, Jean

doi:10.1063/1.1376393

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The Si–H stretching–bending overtone polyads of SiHF₃: Assignments, band intensities, internal coordinate force field, and ab initio dipole moment surfaces

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Breidung, Jürgen
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Thiel, Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Lin, H., Bürger, H., Mkadmi, E. B., He, S.-G., Yuan, L.-F., Breidung, J., et al. (2001). The Si–H stretching–bending overtone polyads of SiHF₃: Assignments, band intensities, internal coordinate force field, and ab initio dipole moment surfaces. The Journal of Chemical Physics, 115(3), 1378-1391. doi:10.1063/1.1376393.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0023-CBF3-4

Abstract

Fourier transform overtone spectra of SiHF were recorded in the region of 2500–9000 cm⁻¹ and vibrationally assigned. Experimental intensities were estimated. The 3ʋ₁ overtone band at 6753 cm⁻¹ was observed to be more than 10 times weaker than the 4ʋ₁ band. A reduced three-dimensional Hamiltonian model in terms of internal coordinates was employed to study the Si–H stretching and bending vibrations including 5ʋ₁ and 6ʋ₁ which were recently recorded using optoacousticspectroscopy. Potential energy parameters were optimized by fitting to experimental band centers. The Fermi resonance between the Si–H stretching and bending motions was found to be insignificant. Band intensities were computed using ab initio one- and three-dimensional dipole momentsurfaces (DMS) expanded to polynomials in terms of symmetrized internal coordinates. The intensity anomaly of 3ʋ₁ is understood as resulting from cancellation of contributions by the linear and quadratic terms in the DMS expansion. The behavior of X–H stretching overtone intensities as excitation increases was also studied in the low and medium energy regions. Whether a rapid or a slow decrease of intensity occurs with increasing excitation depends strongly on the nonlinearity of the DMS. For some molecules, there is an almost complete cancellation of contributions from the lower order terms in the DMS so that the accuracy of the computed overtone intensities is mainly limited by the uncertainty of the higher order expansion coefficients in the DMS.