Half-collision dynamics: Exclusive production of Cd(5s5p 3P2) from the predissociation of Cd(5s5p 1P1)⋅Xe electronic states

Abstract

The CdXe(C 1Π1) state, correlating with Cd(5s5p 1P1)+Xe, undergoes efficient spin–orbit predissociation via the repulsive c̃ 3∑1 state, producing Cd(5s5p 3P2)+Xe exclusively. This is consistent with the fact that the Cd(5s5p 1P1) atomic state is deactivated to Cd(5s5p 3P2 on nearly every collision with a Xe atom. The CdXe(D 1∑+0) state, excited above its dissociation limit, produces not only Cd(5s5p 1P1)+Xe but also a small yield of Cd(5s5p 3P2)+Xe. A mechanism is proposed in which the D 1∑+0 and C 1Π1 states are mixed via rotationally induced L uncoupling, leading to Cd(5s5p 3P2)+Xe by C 1Π1–c̃ 3∑1 predissociation. This has implications related to the dynamical concept of ‘‘orbital following.’’ The dissociation energy D0 of the CdXe(X 1∑+0) ground state is also determined to be 176±5 cm−1.