The effect of the confinement of pi electrons in one- and two-dimensional domains is illustrated with several examples ranging from linear polyene chains to planar molecules with honeycomb structure. Theoretical computations and specific Raman experiments on molecular materials demonstrate that a molecular approach provides a unified key to the interpretation of the Raman response both of linear polyconjugated polymers (polyacetylene) and of nanostructured graphitic materials.
Evidence of the biradicaloid and polyenic character of quinoidal oligothiophenes is reported by proving at the CASSCF//CASPT2 computational level the presence of a low-lying double exciton state responsible for the weak features observed in the NIR absorption region of the longest members of this class of molecules. The energy lowering of this state, accompanying the length increase in the oligomers, causes a displacement of the ground-state equilibrium geometry toward more biradicaloid structures because of the more efficient S0-S1 state mixing. Furthermore, it is shown that the doubly excited state is strongly coupled to the ground electronic state, and the coupling is mediated by a collective mode dominated by the out-of-phase stretching of adjacent CC bonds, recently shown to govern the Raman activity. All together, this evidence offers a unified view of the low-lying electronic states for quinoidal oligothiophenes and polyenes.
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