Isomers of nitric acid and chlorine nitrate

Ab initio molecular orbital calculations at the HF/6-31G* and MP2/6-31G* levels have been performed on nitric acid and chlorine nitrate. Equilibrium geometries and electric dipole moments obtained from the MP2/6-31G* calculations are in good agreement with the respective experimental values, normal-mode (harmonic) vibrational frequencies and frequency shifts due to isotopic substitution calculated at this level support the most recent gas-phase infrared assignments for chlorine nitrate but suggest a reversal in the assignment of v/sub 5/ and v/sub 6/ for nitric acid. Calculations at the same levels of theory were also performed on peroxynitrous acid (HOONO) and chlorine peroxynitrite (ClOONO). The former is found to be 35 kcal/mol less stable than nitric acid at the MP2/6-31G* level; chlorine peroxynitrite is 30 kcal/mol higher in energy than chlorine nitrate. The possible role of these high-energy isomers in atmospheric processes is discussed.