TCB Publications - Abstract

Paul Tavan and Klaus Schulten. The 21Ag - 11Bu energy gap in the polyenes: An extended configuration interaction study. Journal of Chemical Physics, 70:5407-5413, 1979.

TAVA79 For a correct account of the ordering of excited states in the polyenes, in particular the low-lying $2^{1}A_{g}$ and $1^{1}B_{u}$ states, single as well as double excited configurations must be included in a CI expansion. However, for longer $\pi$ systems such expansion shows, in contrast to spectroscopic observations, a divergence of excitation energies and a reversal of the $2^{1}A_{g}$ and $1^{1}B_{u}$ state ordering. We have therefore extended the CI expansion to include all triple and quadruple excitations for the polyene series $C_{n}H_{n+2}$, n = 4,6,8,10,12 and n = 4,6,8,10, respectively. In our calculations we employed a PPP model Hamiltonian. The extended CI expansions correct the faults of previous treatments and predict an increase of the $2^{1}A_{g}$ - $1^{1}B_{u}$ energy gap with increasing polyene length in agreement with recent spectroscopic observations. The effect of higher excitations is mainly due to triple excitations involving three simultaneous spin flips of ground state electrons.

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