Nonadiabatic Electronic Energy Transfer in the Chemical Oxygen-Iodine Laser: Powered by Derivative Coupling or Spin-Orbit Coupling?
Feng AnJunjie ChenXixi HuHua GuoDai-Qian XiePublished in: The journal of physical chemistry letters (2020)
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(2P3/2) + O2(a1Δg) → I(2P1/2) + O2(X3Σg-), 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.
Keyphrases
- energy transfer
- molecular dynamics
- room temperature
- density functional theory
- quantum dots
- single molecule
- ionic liquid
- dual energy
- water soluble
- high speed
- high resolution
- computed tomography
- transition metal
- magnetic resonance imaging
- escherichia coli
- biofilm formation
- climate change
- risk assessment
- pseudomonas aeruginosa
- cystic fibrosis
- electron transfer
- diffusion weighted imaging