Energy Flow Shapes the Decomposition Dynamics of a Reactive Atmospheric Intermediate

Abstract: The unimolecular dynamics of Criegee intermediates depend strongly on their internal energy, which can differ substantially between nascent atmospheric species and laboratory-prepared reactants. Here, the decomposition dynamics of {\it anti-}CH$_3$CHOO are investigated using molecular dynamics simulations on a neural network-based potential energy surface under thermal and mode-selective vibrational excitation. Simulations were performed at internal energies representative of those released during ozonolysis (chemical/thermal preparation, TP) or following vibrational excitation (VibEx) along the CH-stretching mode with two or three quanta, as can be done in laboratory studies. These excitation conditions strongly affect reaction yields and kinetics, with VibEx promoting passage across the initial cyclization barrier. For TP, 35 kcal/mol of internal energy are required to form molecular products, whereas for VibEx, 27 kcal/mol are sufficient. Although TP and VibEx ensembles access largely the same fragmentation pathways with comparable relative yields, the absolute product yields, characteristic timescales, and kinetic behavior differ substantially. Methyldioxirane is found to be a kinetic trap along the pathway. The resulting molecular-level description of {\it anti-}CH$_3$CHOO decomposition provides guidance for interpreting experiments and contributes to a broader understanding of energy-dependent Criegee-intermediate dynamics.