Interpretation of the electronic spectra of four disilanes

Time-dependent density functional theory (TD-DFT/B3LYP(AC)/cc-pVTZ/cc-pVTZ/6-311G//MP2/cc-pVTZ/cc-pVTZ/6-31G**) has been used to compute vertical excitation energies and oscillator strengths of the six low-lying excited states of four peralkylated disilanes, hexamethyldisilane (1), hexa-tert-butyldisilane (2), 1,6-disila4.4.4]propellane (3), and 1,7-disila5.5.5]propellane (4). The results provide an accurate interpretation of the reported UV absorption spectra of 1-4 in solution, and for 1 also in the gas phase up to 62,000 cm(-1). The excellent agreement of the calculated with the available experimental energies and oscillator strengths, and with magnetic circular (MCD) and linear (LD) dichroism, gives us confidence that the method will be useful for dependable interpretation of the electronic spectra of longer oligosilanes. Although the disilane chromophore finds itself in quite different environments in 1-4, its fundamental characteristics remain the same, with one important exception. In all four compounds, the first valence excited state is due to an electron promotion from the sigma(1) HOMO to the pi(1)* orbital, and the second valence excited state to a promotion from the sigma(1) HOMO to the sigma(1)* orbital. Surprisingly, however, it is only in 2, which has an extraordinarily long SiSi bond, that the terminating sigma(1)* orbital is the sigma*(SiSi) antibond, as anticipated, and the sigma sigma* transition has the expected very high oscillator strength. In 1, 3, and 4, the sigma*(SiSi) antibonding orbital is high in energy and does not play any role in low-energy excitations. Instead, the terminating orbital of the sigma(1)sigma(1)* excitation is represented by Si-alkyl antibonds, combined symmetrically with respect to rotation around the SiSi axis and antisymmetrically with respect to operations that interchange the two Si atoms. The common assumption that the characteristic intense sigma sigma* transitions of longer peralkylated oligosilanes extrapolate to the lowest sigma sigma* transition in common peralkylated disilanes is incorrect, and only the weak sigma pi* transitions extrapolate simply.