DFT and AIM study of the protonation of nitrous acid and the pKa of nitrous acidium ion.

The gas phase and aqueous thermochemistry, NMR chemical shifts, and the topology of chemical bonding of nitrous acid (HONO) and nitrous acidium ion (H 2 ONO + ) have been investigated by ab initio methods using density functional theory. By the same methods, the dissociation of H 2 ONO + to give the nitrosonium ion (NO + ) and water has also been investigated. We have used Becke's hybrid functional (B3LYP), and geometry optimizations were performed with the 6-311++G(d,p) basis set In addition, highly accurate ab initio composite methods (G3 and CBS-Q) were used. Solvation energies were calculated using the conductor-like polarizable continuum model, CPCM, at the B3LYP/6-311++G(d,p) level of theory, with the UAKS cavity model. The pK a value of H 2 ONO + was calculated using two different schemes: the direct method and the proton exchange method. The calculated pK a values at different levels of theory range from -9.4 to -15.6, showing that H 2 ONO + is a strong acid (i.e., HONO is only a weak base). The equilibrium constant, K R , for protonation of nitrous acid followed by dissociation to give NO + and H 2 O has also been calculated using the same methodologies. The pK R , value calculated by the G3 and CBS-QB3 methods is in best (and satisfactory) agreement with experimental results, which allows us to narrow down the likely value of the pK a of H 2 ONO + to about -10, a value appreciably more acidic than literature values.