Dedicated to Prof. Clyde Raymond Metz, a good friend and excellent computational chemist, on the occasion of his retirement from the College of Charleston, SC.
Infrared and Raman Spectra, conformations, ab initio calculations and spectral assignments of 1,3-disilabutane (SiH3CH2SiH2CH3)
Version of Record online: 28 APR 2007
Copyright © 2007 John Wiley & Sons, Ltd.
Journal of Raman Spectroscopy
Volume 38, Issue 9, pages 1159–1173, September 2007
How to Cite
Guirgis, G. A., Mazzone, P. M., Pasko, D. N., Klaeboe, P., Horn, A. and Nielsen, C. J. (2007), Infrared and Raman Spectra, conformations, ab initio calculations and spectral assignments of 1,3-disilabutane (SiH3CH2SiH2CH3). J. Raman Spectrosc., 38: 1159–1173. doi: 10.1002/jrs.1745
- Issue online: 22 AUG 2007
- Version of Record online: 28 APR 2007
- Manuscript Accepted: 8 FEB 2007
- Manuscript Received: 15 DEC 2006
- Raman and infrared spectra;
- DFT calculations;
- conformational analysis
Raman spectra of 1,3-disilabutane (SiH3CH2SiH2CH3) as a liquid were recorded at 293 K and as a solid at 78 K. In the Raman cryostat at 78 K an amorphous phase was first formed, giving a spectrum similar to that of the liquid. After annealing to 120 K, the sample crystallized and large changes occurred in the spectra since more than 20 bands present in the amorphous solid phase vanished. These spectral changes made it possible to assign Raman bands to the anti or gauche conformers with confidence. Additional Raman spectra were recorded of the liquid at 14 temperatures between 293 and 137 K. Some Raman bands changed their peak heights with temperature but were countered by changes in linewidths, and from three band pairs assigned to the anti and gauche conformers, the conformational enthalpy difference ΔconfH(gauche–anti) was found to be 0 ± 0.3 kJ mol−1 in the liquid. Infrared spectra were obtained in the vapor and in the liquid phases at ambient temperature and in the solid phases at 78 K in the range 4000–400 cm−1. The sample crystallized immediately when deposited on the CsI window at 78 K, and many bands present in the vapor and liquid disappeared. Additional infrared spectra in argon matrixes at 5 K were recorded before and after annealing to temperatures 20–34 K. Quantum chemical calculations were carried out at the HF, MP2 and B3LYP levels with a variety of basis sets. The HF and DFT calculations suggested the anti conformer as the more stable one by ca 1 kJ mol−1, while the MP2 results favored gauche by up to 0.4 kJ mol−1. The Complete Basis Set method CBS-QB3 gave an energy difference of 0.1 kJ mol−1, with anti as the more stable one. Scaled force fields from B3LYP/cc-pVQZ calculations gave vibrational wavenumbers and band intensities for the two conformers. Copyright © 2007 John Wiley & Sons, Ltd.