Theoretical Studies on the Isomerization of Peroxynitrite to Nitrate Mediated by Peroxynitrous Acid

【摘要】 The conversion of peroxynitrite (ONOO-) to nitrate (NO3-) mediated by peroxy- nitrous acid (ONOOH) has been investigated at the CCSD/6-311G(d)//B3LYP/6-311+G(d,p) level. Two kinds of pathways for the title reaction were found. The results show that the energy barrier of isomerization through pathway 1 is around 25 kcal/mol in the gas phase. This value is significantly lower than that of isomerization without any catalysts. Thus, it indicates that ONOOH definitely makes the conversion from ONOO- to NO3- feasible. Although pathway 2 does not decrease the energy barrier of this isomerization, peroxynitric acid (O2NOOH) was obtained; moreover, this is a new pathway for this formation. In view of the results that peroxynitrate anion can decompose into nitrite and dioxygen, we conclude that our results are consistent with the experimental observation that nitrate, nitrite, and dioxygen are the main final products of the decay of peroxynitrite around pH 7.更多还原

【Abstract】 The conversion of peroxynitrite (ONOO-) to nitrate (NO3-) mediated by peroxy- nitrous acid (ONOOH) has been investigated at the CCSD/6-311G(d)//B3LYP/6-311+G(d,p) level. Two kinds of pathways for the title reaction were found. The results show that the energy barrier of isomerization through pathway 1 is around 25 kcal/mol in the gas phase. This value is significantly lower than that of isomerization without any catalysts. Thus, it indicates that ONOOH definitely makes the conversion from ONOO- to NO3- feasible. Although pathway 2 does not decrease the energy barrier of this isomerization, peroxynitric acid (O2NOOH) was obtained; moreover, this is a new pathway for this formation. In view of the results that peroxynitrate anion can decompose into nitrite and dioxygen, we conclude that our results are consistent with the experimental observation that nitrate, nitrite, and dioxygen are the main final products of the decay of peroxynitrite around pH 7.更多还原