State selective reactions prepared through the excitation of orbital states in van der Waals complexes of Ca–HX*

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Abstract
We have observed the chemiluminescent reaction Ca*+HX→CaX*+H, where the reactants are prepared in a van der Waals complex formed in a supersonic expansion. This preparation, combined with tunable laser excitation, allows access to well‐defined electronic states of the reaction complex corresponding to different orientations of the calcium excited orbital. In the case of the Ca–HBr complex, a remarkable effect of this preparation is observed on the branching ratio to the final excited states A 2Π and B 2Σ of CaBr: Depending upon the selected state of the complex, the A/B ratio varies by a factor of 2. This is interpreted by the conservation of the orbital orientation during the reaction involving the departure of the hydrogen.