Ab initio study of the electronic structures and conduction properties of some novel low band-gap donor–acceptor polymers

The results of the electronic structures and conduction properties of four novel donor–acceptor polymers based on polysilole, obtained on the basis of ab initio Hartree–Fock crystal orbital method using their optimized geometries, are reported. The repeat unit of these polymers consists of bicyclopentadisilole unit bridged by an electron-accepting group Y(Y=CCH2 in PSICH, CO in PSICF, CCF2 and CC(CN)2 in PSICN). All the polymers on the basis of their geometries and π-bond order values are found to have benzenoid-type electronic structures. Comparison of the important electronic properties such as ionization potential, electron affinity and band-gap of these polymers indicates PSICN to be the best candidate for intrinsic conductivity and reductive (n-) doping while PSICH is predicted to be the best candidate for oxidative (p-) doping. All these polymers are estimated to have band-gap values ranging between 1 and 2 eV. The low band-gap values of these polymers are rationalised on the basis of the patterns of their frontier orbitals.