Electronic excitations in finite and infinite polyenes

Abstract

We study electronic excitations in long polyenes, i.e., in one-dimensional strongly correlated electron systems which are neither infinite nor small. The excitations are described within Hubbard and Pariser-Parr-Pople (PPP) models by means of a multiple-reference double-excitation expansion [P. Tavan and K. Schulten, J. Chem. Phys. 85, 6602 (1986)]. We find that quantized ``transition'' momenta can be assigned to electronic excitations in finite chains. These momenta link excitation energies of finite chains to dispersion relations of infinite chains, i.e., they bridge the gap between finite and infinite systems. A key result is the following: Excitation energies E in polyenes with N carbon atoms are described very accurately by the formula ${E}^{\ensuremath{\beta}}$=\ensuremath{\Delta}${E}_{0}^{\ensuremath{\beta}}$+${\ensuremath{\alpha}}^{\ensuremath{\beta}}$k(N)q, q=1,2,..., where \ensuremath{\beta} denotes the excitation class, \ensuremath{\Delta}${E}_{0}^{\ensuremath{\beta}}$ the energy gap in the infinite system [${\ensuremath{\alpha}}^{\ensuremath{\beta}}$k(N)>0], and k(N) the elementary transition momentum. The parameters \ensuremath{\Delta}${E}_{0}^{\ensuremath{\beta}}$ and ${\ensuremath{\alpha}}^{\ensuremath{\beta}}$ are determined for covalent and ionic excitations in alternating and nonalternating polyenes. The covalent excitations are combinations of triplet excitations T, i.e., T, TT, TTT, . . . . The lowest singlet excitations in the infinite polyene, e.g., in polyacetylene or polydiacetylene, are TT states. Available evidence proves that these states can dissociate into separate triplets. The bond structure of TT states is that of a neutral soliton-antisoliton pair. The level density of TT states in long polyenes is high enough to allow dissociation into separate solitons.