Relaxation energies and excited-state structures of poly(paraphenylene)

We investigate the relaxation energies and excited state geometries of the light emitting polymer, poly(paraphenylene). We solve the Pariser-Parr-Pople-Peierls model using the density matrix renormalization group method. We find that the lattice relaxation of the dipole-active 1(1)B(1u)(-) state is quite different from that of the 1(3)B(1u)(+) state and the dipole-inactive 2(1)A(g)(+) state. In particular, the 1(1)B(1u)(-) state is rather weakly coupled to the lattice and has a rather small relaxation energy similar to 0.1 eV. In contrast, the 1(3)B(1u)(+) and 2(1)A(g)(+) states are strongly coupled with relaxation energies of similar to 0.5 and similar to 1.0 eV, respectively. By analogy to linear polyenes, we argue that this difference can be understood by the different kind of solitons present in the 1(1)B(1u)(-), 1(3)B(1u)(+), and 2(1)A(g)(+) states. The difference in relaxation energies of the 1(1)B(1u)(-) and 1(3)B(1u)(+) states accounts for approximately one-third of the exchange gap in light-emitting polymers.