Abstract
Carbon occurs in many different polymeric forms, but nitrogen and oxygen do not. Beginning with the hydrogen polyoxides of general formula H2On, we look into the reasons for this observation. Calculations show that the geometry of an oxygen chain is in the form of a helix, and that there is a minimum bond dissociation energy for an oxygen chain which contains six oxygen atoms. Most surprisingly, longer chains are harder to break. A similar analysis applies to nitrogen chains, except that they are predicted to be more stable than their oxygen counterparts. In solution, however, proton transfer mechanisms provide low-energy paths to decomposition which explains why the polyoxide and polynitride chains have not been observed experimentally. We also look at another polymeric form of nitrogen in the form of a perfect icosahedron (‘dodecahedrazane’). We predict that long-chain polymers could be formed by linking together these nitrogen clusters with carbon connectors. The synthetic difficulties to create new compounds such as these will be formidable, but one possible outcome is a totally pollution-free fuel based on polymeric nitrogen.