Lower-lying potential curves of Br2 are calculated by the spin-orbit configuration interaction method, and the spin-orbit branching mechanisms in the photodissociation processes are examined. The second absorption band at 227 nm is assigned unambiguously to the transition from the X1Σ+g to the 3Σ+1u (σg→σu* state. The calculated potential curves and the radial derivative coupling elements of Cl2 and Br2 are used to evaluate the nonadiabatic transition probabilities by solving the time-dependent coupled Schrödinger equations semiclassically. The different nonadiabatic behavior in Cl2 and Br2 is analyzed in terms of the differences in the electronic factors and the reduced mass.
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