First-principles calculations on adiabatic potential surfaces of hydrogen atoms in polysilane

Adiabatic potential surfaces are calculated for an H atom at various positions in polysilane. The calculations are based on local-density-functional theory, using pseudo-potentials, in a supercell geometry. The migration paths for a H atom dissociated from the side-chain position, and for a foreign H atom are investigated. One possible path entwines the Si skeleton. Bond switching due to breaking the Si-H bond and the ensuing H migration is also discussed on the basis of three hypothetical atomic configurations.