Density functional theory and ab initio study of bond dissociation energy for peroxonitrous acid and peroxyacetyl nitrate

Geometries and energies of two nitro peroxides, HOONO2 and CH3COOONO2 are calculated by two common ab initio (ROHF and MP2), local (SVWN), four hybrid (BHandH, BHandHLYP, Becke3LYP, and Becke3P86) and two non-local (BLYP and BP86) density functional theory (DFT) methods. In all calculations standard GAUSSIAN-type basis sets [6-31+G(d) and 6-311++G(3df,3pd)] are used. Based on the comparison of computed and experimental values both Becke3LYP hybrid and BLYP non-local DFT methods generate energies that are in excellent agreement with experimental values. The suitability of other methods for computing these and similar molecules are discussed.