Abstract: J. Chem. Phys. 120 (2004) 11910-11918

Ch. Willnauer and U. Birkenheuer
Quantum Chemical ab-initio Calculations of Correlation Effects in Complex Polymers: Poly(para-phenylene)
J. Chem. Phys. 120 (2004) 11910-11918
[Jun 22, 2004]


Different quantum chemical approaches to the ground state correlation energy per unit cell of infinite poly(para-phenylene) (PPP) chains are presented. PPP is an organic polymer with interesting optical properties, due to its conjugated, aromatic p system. The inclusion of correlation effects is crucial for a sound quantum chemical description of such a system. The correlation calculations were performed on the coupled cluster with single and double excitations (CCSD) level of theory using Dunning's spd correlation consistent polarized valence double-zeta basis sets. The correlation energy per unit cell is determined by means of the incremental method, which comprises series of CCSD calculations with partial excitation spaces. The resulting correlation energy per unit cell of PPP is -21.797 eV and compares well with that obtained by a simple but much more demanding cluster convergence approach (-21.775 eV). In addition, the accuracy and performance of the incremental scheme is discussed with respect to full CCSD benchmark calculations on PPP oligomers. Two variants are considered, the conventional one based on bond-type local units, and an extended one based on natural chemical subunits. Whereas it is difficult to reach "chemical" accuracy with the first variant, the second variant allows an accurate and efficient treatment with only a few individual CCSD calculations for a polymer with an aromatic p system such as PPP.