The rovibronic spectrum of the Na3B system is computed taking into account full rovibronic coupling between different vibronic states. The rovibronic coupling matrix elements are calculated using the vibronic states following from a pseudo Jahn–Teller model for the vibronic dynamics in the B system. Comparison with results of optical–optical double resonance measurements [W. E. Ernst and S. Rakowsky, Can. J. Phys. 72, 1307 (1994)] shows good agreement. In particular, certain properties of the Coriolis splittings, so far explained by an ad hoc spin–rotation interaction, are now well understood as the consequence of rovibronic coupling between two vibronic states. A general discussion of rovibronic dynamics on electronic potential energy surfaces with three equivalent minima is presented.

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