Density-matrix renormalization-group calculations of excited states of linear polyenes - art. no. 195108

We present density-matrix renormalization-group calculations of the Pariser -Parr-Pople-Peierls model of linear polyenes within the adiabatic approxima tion. We calculate the vertical and relaxed transition energies, and relaxe d geometries for various excitations on long chains. The triplet (1 B-3(u)) and even-parity singlet (2 (1)A(g)(+)) states have a 2-soliton and 4-soli ton forms. respectively, both with large relaxation energies. The dipole-al lowed (1 B-1(u)-) state forms an exciton-polaron, and has a very small rela xation energy. The relaxed energy of the 2 (1)A(g)(+) state lies below that of the 1 B-1(u)- state. We observe an attraction between the soliton-antis oliton pairs in the 2 (1)A(g)(+) state. The calculated excitation energies agree well with the observed values for polyene oligomers; the agreement wi th polyacetylene thin films is less good, and we comment on the possible so urces of the discrepancies. The photoinduced absorption is interpreted. The spin-spin correlation function shows that the unpaired spins coincide with the geometrical soliton positions. We study the roles of electron-electron interactions and electron-lattice coupling in determining the excitation e nergies and soliton structures. Electronic interactions play the key role i n determining the ground-state dimerization and the excited-state transitio n energies.