Large-scale correlated calculations of linear optical absorption and low-lying excited states of polyacenes: Pariser-Parr-Pople Hamiltonian

Abstract

We present large-scale correlated calculations of the linear optical absorption spectrum of oligo-acenes containing up to seven benzene rings. For the calculations we used the Pariser-Parr-Pople (PPP) Hamiltonian, along with the configuration interaction (CI) technique at various levels such as the full CI, the quadruple CI, and multireference singles-doubles CI. The role of Coulomb parameters used in the PPP Hamiltonian was examined by considering standard Ohno parameters, as well as a screened set of parameters. A detailed analysis of the many-body character of the important excited states contributing to the linear absorption has also been performed. The results of our calculations have been compared extensively with the theoretical work of other authors, as well as with experiments.