Role of surface crossings in the photochemistry of nitromethane

Abstract

The photodissociation dynamics of nitromethane (CH(3)NO(2)) starting at the S(3) excited state has been studied at the complete active space self-consistent field level of theory in conjunction with atomic natural orbital type basis sets. In addition, the energies of all the critical points and the energy profiles connecting them have been recomputed with the multiconfigurational second-order perturbation method. It is found that the key step in the reaction mechanism is a radiationless decay through an S(3)S(2) conical intersection. The branching space spanned by the gradient difference and nonadiabatic coupling vectors of this crossing point comprises dissociation into excited nitromethane plus singlet atomic oxygen [CH(3)NO(1A")+O((1)D)] and S(3)-->S(2) deactivation, respectively. Furthermore, deactivated nitromethane S(n (n<3)) can decompose in subsequent steps into CH(3)+NO(2), where NO(2) is generated at least in two different electronic states (1 (2)B(2) and 1 (2)A(1)). It is shown that formation of excited nitric oxide NO(A (2)Sigma) arises from CH(3)NO(1A") generated in the previous step. In addition, four crossings between singlet and triplet states are localized; however, no evidence is found for a relevant role of such crossings in the photochemistry of CH(3)NO(2) initiated at S(3) state in the gas phase.