Mini‐bandstructure tailoring in π‐conjugated periodic block copolymers using the envelope crystalline‐orbital method

A strategy for the systematic design of polymeric superlattices with tailor‐made mini‐bandgaps and carrier mini‐effective masses is described and computationally implemented by means of an envelope crystalline‐orbital method, which is a straightforward adaptation for molecules of the envelope‐function approximation widely used in solid‐state physics. Such strategy relies on the construction of π‐conjugated periodic block copolymers from well‐characterized parent polymers, in such a way that the aforementioned electronic parameters can be predicted from the lengths of the blocks. Illustrative calculations for prototypical (PPP_x‐PDA_y)_n superlattices demonstrate the plausibility of the strategy and the advantages of the computational implementation used. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2532–2540, 2010