Infrared intensities of some SiH-containing compounds in the gas-phase.
Infrared intensities measured in the gas-phase are reported for CH3SiH3, CH3SiD3, (CH3)2SiH2, (CH3)2SiD2, (SiH3)2CH2, (SiD3)2CH2, Si2H6, SiH2Cl2 and (SiH3)2O. These are compared with theoretical estimates from HF, MP2 and B3LYP calculations with the 6-311G** basis set. Literature values of nuCH intensities per bond from 18 compounds correlate linearly with the values calculated at MP2 and B3LYP levels: the corresponding HF plot is slightly curved. The new HC(Si) data fit these correlations adequately. In similar plots for SiH stretching intensity, the point for SiH2Cl2 is displaced, especially at the HF level. The lack of relation of nuCH or nuSiH intensity to Mulliken atomic charge points to the effect of varying atomic charge flux in the parameter thetamu/thetar. Anomalies associated with nuSiH intensities influenced by chlorine or OR substitution and previously explained by d(pi)-p(pi) bonding are attributed instead to charge flux variation. For silyl groups, deformation band intensities are roughly additive according to the number of such groups. However, this is not the case for the methyl symmetric deformation bands in methyl and dimethyl silanes.
Coats
A M
AM
Department of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, UK.
McKean
D C
DC
D008958:Models, Molecular; D011789:Quantum Theory; D012825:Silicon / Q000737:chemistry*; D017655:Silicon Compounds / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
D017655:Silicon Compounds; D012825:Silicon