Matrix-isolation IR and UV spectra of Si3H8 and Si4H10: Isomers and conformers of oligosilanes

Journal article, 1996

Matrix-isolation IR and UV spectra of Si3H8, i-Si4H10, and the two conformers of n-Si4H10 have been recorded. A quantitative separation of the IR spectrum of n-Si4H10 into contributions from the anti and gauche forms was accomplished by a combination of matrix annealing and selective monochromatic photodestruction experiments. A qualitative separation of their UV spectra was achieved as well. The IR spectra of Si3H8, i-Si4H10, and the two conformers of n-Si4H10 have been assigned by comparison with results of ab initio calculations, which reproduce the frequencies and even the relative intensities quite well. The calculations predict dihedral angles omega of 180 degrees and 57 degrees for the anti and the gauche conformer of n-Si4H10, respectively, and confirm earlier predictions of nearly equal stability for an isolated molecule. In the matrix, the anti conformer is more stable, The conformational effects on the UV spectrum of n-Si4H10 are not those anticipated from simple models of the Sandorfy or ladder C type, in that it is primarily not the energy but the intensity of the low-energy excited singlet states that depends strongly on the SiSiSiSi dihedral angle omega. This result is interpreted in terms of data from 6-in-8 CASSCF 6-31G* calculations, which predict an avoided crossing between a strongly allowed sigma sigma* B state and a very weakly allowed sigma pi* B state as omega changes, with the former lower in energy at 180 degrees and the latter lower at 0 degrees. Consequences for attempts to understand the effects of conformation on optical spectra of polysilanes are noted.