AN APPLICATION OF QUANTUM-CHEMISTRY TO THE SEARCH FOR NEW MATERIALS -METASTABLE POLYMERS FORMED AT HIGH-PRESSURES

MNDO/AM1 studies indicate the possibility of forming metastable polyme rs of nitrogen oxides, through application of the extreme pressures wh ich have become accessible in recent years. Kinetically stable open-ch ain polymers of nitric oxide, (NO)x, analogous to the known polythiazy l, (SN)x, and/or (ONNO)x, and polycyclic (ONNO)x, may be obtainable. O f particular interest is the possibility of forming a planar, cis, tra ns open-chain polymer of nitrous oxide, which is geometrically quite s imilar to (SN)x. As offshoots of the investigations, it is found that: (1) a polycyclic derivative, (SNNS)x, may be formed exothermically fr om (SN)x, and possess superior conducting properties; (2) marriage of a hypothetical cyclic trimer of nitric oxide and an open-chain polymer of nitrous oxide may account for experimental investigations which ha ve reported a preponderance of the (NO)3(ONN)x+ cations in mass-spectr ometric studies of mixtures of nitric and nitrous oxides; (3) an inter esting series of strain-free cage compounds, N6O6, N6S6, and N12H6, Wh ich are isostructural with the skeleton of the known hydrocarbon icean e, C12H18 may be realizable; (4) high-energy cyclic oligomers of nitro us oxide, (N2O)2-6, which are similar to crown ethers, and whose deriv atives might form a novel series of sequestering agents or gas generat ors, are possible.