Excitons in conjugated polymers: Wavefunctions, symmetries, and quantum numbers

We introduce a mapping from configuration interaction singles wavefunctions, expressed as linear combinations of particle-hole excitations between Hartree-Fock molecular orbitals, to real-space exciton wavefunctions, expressed as linear combinations of particle-hole excitations between localized Wannier functions. The exciton wavefunction is a two-dimensional amplitude for the exciton center-of-mass coordinate, R, and the electron-hole separation (or relative coordinate), r, having an exact analogy to one-dimensional hydrogenlike wavefunctions. We describe the excitons by their appropriate quantum numbers, namely, the principle quantum number, n, associated with r and the center-of-mass pseudomomentum quantum number, j, associated with R. In addition, for models with particle-hole symmetry, such as the Pariser-Parr-Pople model, we emphasize the connection between particle-hole symmetry and particle-hole parity. The method is applied to the study of excitons in trans-polyacetylene and poly (para-phenylene). (C) 2008 American Institute of Physics. [DOI: 10.1063/1.3001584]