Separate coupled-channel Schrödinger-equation (CSE) models of the interacting (1)Pi(u) (b,c,o) and (3)Pi(u) (C,C(')) states of N(2) are combined, through the inclusion of spin-orbit interactions, to produce a five-channel CSE model of the N(2) predissociation. Comparison of the model calculations with an experimental database, consisting principally of detailed new measurements of the vibrational and isotopic dependence of the (1)Pi(u) linewidths and lifetimes, provides convincing evidence that the predissociation of the lowest (1)Pi(u) levels in N(2) is primarily an indirect process, involving spin-orbit coupling between the b (1)Pi(u)- and C (3)Pi(u)-state levels, the latter levels themselves heavily predissociated electrostatically by the C(') (3)Pi(u) continuum. The well-known large width of the b(v=3) level in (14)N(2) 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 (1)Pi(u) states of N(2), and is thus likely to prove useful in the construction of realistic radiative-transfer and photochemical models for nitrogen-rich planetary atmospheres.
New and existing spectroscopic data on N(2), obtained using a wide variety of experimental techniques, are interpreted using a coupled-channel Schrodinger-equation (CSE) model of the structure and predissociation dynamics for the interacting Rydberg and valence states of (3)Pi(u) symmetry. As a result, v>0 levels of the 3ppi(u)G(3) (3)Pi(u) Rydberg state are assigned correctly for the first time, leading to the identification of very strong perturbations in the G(3)-state vibrational structure. A four-channel CSE model, which includes the 3ssigma(g)F(3) (3)Pi(u) and 3ppi(u)G(3) (3)Pi(u) Rydberg states and the C(') (3)Pi(u) and C (3)Pi(u) valence states, indicates strong Rydberg-Rydberg coupling between the F(3) and G(3) states, strong Rydberg-valence coupling between the G(3) and C(') states, and weaker coupling between the F(3) and C(') states.
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