title: Isomerization Pathways of ONCNO: Unstable or Metastable?
abstract: Fulminates containing the CNO(-) ion have been widely utilized as high-energy density materials (HEDMs) for more than 120 years. Yet no purely covalently bound CNO molecule, i.e., nitrile oxide, is known to behave as an HEDM. In this study, we performed a thorough investigation of the potential energy surface of nitrile oxide ONCNO and related isomers, applying various sophisticated methods including G4, CBS-QB3, W1BD, CCSD(T)/CBS, and CASPT2/CBS. The Gibbs free energy calculations showed that the decomposition of ONCNO to the considerably endothermic products CNO + NO is favored compared to that into the highly exothermic products CO2 + N2. Thus, ONCNO fails to be the long expected nitrile oxide HEDM. However, with the rate-determining barrier of 23.3 kcal mol(-1) at the W1BD level, ONCNO should be experimentally accessible.
authors: Institute of Theoretical Chemistry, Jilin University , Changchun 130023, People's Republic of China.
authors: Fei-Fei
authors: FF
authors: He
authors: College of Chemistry and Chemical Engineering, Northeast Petroleum University , Daqing 163318, PR China.
authors: Si-Meng
authors: SM
authors: Gao
authors: Dipartimento di Chimica e Tecnologie del Farmaco, "Sapienza" University of Rome , P.le Aldo Moro 5, 00185 Roma, Italy.
authors: Giulia de
authors: Gd
authors: Petris
authors: Dipartimento di Ingegneria Civile e Ambientale, University of Perugia and ISTM-CNR , Via Duranti 93, 06125 Perugia, Italy.
authors: Marzio
authors: M
authors: Rosi
authors: Institute of Theoretical Chemistry, Jilin University , Changchun 130023, People's Republic of China.
authors: Yi-Hong
authors: YH
authors: Ding