Indexed on: 01 Jun '12Published on: 01 Jun '12Published in: Journal of Physical Chemistry A
To explore the dynamics of OH formation from two photon absorbed NO(2) with H(2)O, a high-level multiconfigurational perturbation theory was used to map the potential energy profiles of NO(2) dissociation to O ((1)D) + NO (X(2)Π), and subsequent hydrogen abstraction producing 2OH (X(2)Π) + NO (X(2)Π) in the highly excited S(PP) (Ẽ(2)A', (2)ππ*) state. The ground state NO(2) is promoted to populate in the S(NP1) (Ã(2)A", (2)nπ*) intermediate state by one photon absorption at ~440 nm, one thousandth of which is further excited to S(PP) (Ẽ(2)A', (2)ππ*) state and undergoes a medium-sized barrier (~11.0 kcal/mol) to give rise to OH radicals. In comparison with the hydrogen abstraction reaction in highly vibrationally excited NO(2) ground state, two photon absorption facilitates NO(2) dissociation to O ((1)D) and O ((1)D) + H(2)O → 2OH (X(2)Π) but results in low quantum yield of NO(2)** since there is a weak absorption upon the second beam light at ~440 nm. It can be concluded that the reaction of two photon absorbed NO(2) with H(2)O makes negligible contributions to the formation of OH radicals. In contrast, single photon absorption at <554 nm is a possible process on the basis of the present and previous computations.