Abstract
We interpret the reversal of the direction of the thermochromic shift of the first absorption band of peralkylated oligosilanes as the silicon chain is extended, based on multistate complete active space second-order perturbation theory (MS-CASPT2) calculations for octamethyltrisilane, Si3Me8. The observed shift is attributed to the effect of b1 distortions from ground state equilibrium geometry on vertical excited state energies and intensities. A generally contracted basis set of atomic natural orbitals (ANOs) at a ground state geometry optimized in the second-order Møller–Plesset perturbation theory (MP2) approximation with Dunning's correlation consistent triple-zeta basis set (cc-pVTZ) for the silicon atoms, the 6-31G* set for the carbon atoms and the 6-31G set for the hydrogen atoms was used. §This paper is dedicated to Professor Michael A. Robb on the occasion of his 60th birthday.
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