Conformation study of helical main-group polymers: organic and inorganic, trans and gauche

Abstract

In this paper electronic structures of some helical polymers, which range from typical organic polymers such as polyethylene and poly(oxymethylene) to standard inorganic polymers such as polymeric sulfur to main-group (P, B, etc.) atomic chains in crystals (such as NaP, CrB, etc.), have been investigated by means of our helical modifications of solid-state band theory programs based on modified neglect of diatomic overlap (MNDO) and extended Hueckel theory (EHT). The analysis of orbital interactions shows that the all-trans conformation for the polymer with either less or more than six valence electrons in the repeat unit is energetically favorable as compared with the gauche conformation while the polymers having valence electrons close to six in the repeat unit are more likely to be found in a gauche conformation, except for polyethylene and polysilane, for which both conformations are stable. The stability of all-trans-polyethylene and -polysilane is attributed to the weak repulsions between C-H and Si-H bonding electron pairs. A quadratic relationship between band width and the corresponding closed-shell repulsion for an energy band is established.