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.
Dissociations of the ethyne dication following its production by photoionization in the photon energy range of 35–65 eV have been investigated by the photoelectron–ion–ion coincidence technique using both synchrotron radiation and laboratory light sources. New quantum mechanical calculations identify and locate the electronic states of the molecular dication in this energy range and show that the dissociation products are formed in their ground states by heterogeneous processes. Five reaction channels leading to three molecular fragments have been identified and are interpreted as sequential processes, several faster than fragment rotation and one possibly involving dissociation of CH+ to H+ with a lifetime of the order of 25 fs.
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