Transition probabilities of H2, HD, and D2 − electric dipole, − discrete-continuum magnetic dipole, and electric quadrupole transitions have been calculated using accurate energies and ro-vibrational wave functions obtained from precise ab initio potential energy curves. The predissociation rates of the () levels by direct and indirect spin–spin and spin–orbit coupling between − fine structure levels, have been also determined. The present investigation achieved good agreement with measured lifetimes of the fine structure levels without adjustment. A comparison of the calculated and observed lifetimes of metastable H2, HD, and D2 suggests that the − magnetic dipole and electric quadrupole transition moments underestimate the spontaneous emission rate of the metastable levels by ∼370 s−1. The measured and calculated lifetimes of H2, HD, and D2 fine structure levels are in very good agreement after the adjustment of 370 s−1 to the spontaneous decay rate of the − transition. The calculated energies, transition probabilities, and predissociation rates obtained in the present work, along with the state excitation function, are sufficient to determine the state emission cross section, the kinetic energy distribution of H(1s) atoms, and the energy deposition rate of the − excitation. In a previous investigation by Berg and Ottinger (1994 J. Chem. Phys. 100 8746), the authors were forced to insert a large scale factor into the predissociation rate in order to reconcile with measured lifetimes. Errors introduced in the approximations made in the previous investigations are discussed in the text. The H2 state has the second largest triplet state excitation cross section. Predissociation and spontaneous emission of the state plays an important role in the energy deposition of H2-dominated atmospheres.
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