Nonadiabatic Electronic Energy Transfer in the Chemical Oxygen–Iodine Laser: Powered by Derivative Coupling or Spin–Orbit Coupling?

Abstract

Derivative couplings near a conical intersection and spin-orbit couplings between different spin states are known to facilitate nonadiabatic transitions in molecular systems. Here, we investigate a prototypical electronic energy transfer process, I(²<i>P</i>_3/2) + O₂(<i>a</i>¹Δ_<i>g</i>) → I(²<i>P</i>_1/2) + O₂(<i>X</i>³Σ_<i>g</i>^-), which is of great importance for the chemical oxygen-iodine laser. To understand the nonadiabatic dynamics, this multistate process is investigated in full dimensionality with quantum wave packets using diabatic potential energy surfaces coupled by both derivative and spin-orbit couplings, all determined from first principles. A near quantitative agreement with structural, energetic, and kinetic measurements is achieved. Detailed analyses suggest that the nonadiabatic dynamics is largely controlled by derivative coupling near conical intersections, which leads to a small effective barrier and hence a slightly positive temperature dependence of the rate coefficient. The new results should extend our understanding of energy transfer, provide a quantitative basis for numerical simulations of the chemical oxygen-iodine laser, and have important implications in other electronic energy transfer processes.