Charge-doped and heteroatom-substituted polysilane, poly(vinylenedisilanylene), and poly(butadienylenedisilanylene): electronic structures and band gaps.

The effects of charge-doping and boron and phosphorus substitution on the electronic structures and band gaps of polysilane, poly(vinylenedisilanylene), and poly(butadienylenedisilanylene) were theoretically investigated by using density functional theory and time-dependent density functional theory. Band gaps of polymers were estimated both by extrapolations from excitation energies of oligomers up to 30 units and by calculations with the periodic boundary condition. It was found that charge-doping in the polysilane decreases the band gap more significantly than B and P substitutions. However, Si-Si bonds are easily broken by charge-doping. In contrast, B and P substitutions exert little influence on the strength of Si-Si bonds. From natural bond orbital analysis, it was concluded that charge-doping and heteroatom substitution bring about a lowering of the band gap in sigma conjugated polysilanes because of strong electron-hole interactions. The introduction of longer pi conjugated moieties was found to reduce band gaps of sigma-pi conjugated chains. In contrast to the sigma conjugated polysilanes, bridged structures and a different distribution of polarons were found in cations of sigma-pi conjugated chains.