NUMERICAL APPLICATION OF THE COUPLED CLUSTER THEORY WITH LOCALIZED ORBITALS TO POLYMERS .4. BAND STRUCTURE CORRECTIONS IN MODEL SYSTEMS AND POLYACETYLENE

摘要

We present the formalism for the correction of the band structure for correlation effects of polymers in the framework of a localized orbital approximation, using the quasiparticle model. For this purpose we use in an ab initio framework Moller-Plesset perturbation theory in second order, the coupled cluster doubles method, and its linear approximation. The formalism is applied to a water stack and two different forms of a water chain as model systems to test the reliability of the approximations involved. From our previous work we know that, e.g., in polyacetylene difficulties due to the localizability of the canonical crystal orbitals do not arise from the pi or pi* hands, but from bands of sigma symmetry. Thus we concentrate in this work again on polyacetylene as an example of a realistic polymer. We find that the localized orbital approximation is quite useful also in the case of band structure corrections due to correlation effects. However, the coupled cluster calculations, in particular, turn out to be computationally very costly for infinite systems. But it seems to us that Localized orbital approximations are at the moment the only way to make coupled cluster calculations on realistic polymers with covalent bonds between the unit cells possible at all. (C) 1997 American Institute of Physics. [References: 100]