Electronic energy partitioning in reactions occurring on more than one potential energy surface: Metastable Mg(3P) atoms with halogen molecules

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Abstract
For the reactions metastable Mg(3P) atoms and dihalogen molecules F2, Cl2, and Br2 we have measured by a beam‐gas experiment the absolute cross sections for all three electronic reaction channels: formation of MgX(X 2Σ+) ground state, MgX(A 2Π) chemiluminescent products and MgX+(1Σ+) chemi‐ions. The chemiluminescence and chemi‐ion yields both turn out to be of the order of 1% in all three systems. By qualitative MO theory, it is shown that the dynamical bottleneck in the adiabatic chemiluminescence channel is an early barrier and in the diabatic chemi‐ionization process a spin flip occurring during the approach phase, following a long‐range electron transfer. An information theoretic analysis reveals considerable dynamic bias associated with most of the CL and CI products [except for MgCl (A 2Π)], and the surprisal plots are nonlinear for all three reactions.

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