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In this paper we investigate the dynamics of orbiting complex formation in Na+/N2 collisions using classical trajectories. We first demonstrate that the rigid-rotor approximation is appropriate for computing complex formation probabilities and lifetimes, as the NZ vibration is weakly coupled to the other degrees of freedom. For a collision ensemble with zero impact parameter and total angular momentum J = 0, complex formation probabilities exhibit oscillatory behavior with E. Several differentdoi:10.1021/j100009a001 fatcat:tbcmdyno6zby5bbdu7gzrjzh6i