A theoretician's view of the Ce+ mediated activation of the NH bond in ammonia

► Ce+ mediated activation of the NH bond in ammonia is a typical 'two-state reaction' (TSR). ► Hydrogen-elimination reaction of ammonia is favorable to the thermodynamics but is unfavorable to the dynamics. ► A full natural bond orbital analysis was performed to understand of the activation of the NH bond. ► Crossing points between the potential energy surfaces are located using different methods. ► The large value of PISC estimated shows that the ISC occurs with a great probability.