MS-CASPT2 analysis of the UV thermochromism of octamethyltrisilane

2006

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 Moller–Plesset perturbation theory (MP2) approximation with Dunning's correlation consistent triple-zeta basis set (cc-pVTZ)…