Predissociation mechanism for the lowest ¹Πu states of N₂

Abstract

Separate coupled-channel Schrödinger-equation (CSE) models of the interacting ¹Πu (b,c,o) and ³Πu (C,C′) states of N₂ are combined, through the inclusion of spin-orbit interactions, to produce a five-channel CSE model of the N₂predissociation. Comparison of the model calculations with an experimental database, consisting principally of detailed new measurements of the vibrational and isotopic dependence of the Πu1linewidths and lifetimes, provides convincing evidence that the predissociation of the lowest ¹Πu levels in N2 is primarily an indirect process, involving spin-orbit coupling between the b¹Πu- and C³Πu-state levels, the latter levels themselves heavily predissociated electrostatically by the C′³Πu continuum. The well-known large width of the b(v=3) level in ¹⁴N₂ is caused by an accidental degeneracy with C(v=9). This CSE model provides the first quantitative explanation of the predissociation mechanism for the dipole-accessible ¹Πu states of N₂, and is thus likely to prove useful in the construction of realistic radiative-transfer and photochemical models for nitrogen-rich planetary atmospheres.