End-to-End Photodissociation Dynamics of Energized H$_2$COO

TL;DR

This study uses neural network-based molecular dynamics simulations to quantitatively analyze the reaction pathways and product distributions of energized H$_2$COO, revealing detailed dynamics and branching ratios relevant to atmospheric chemistry.

Contribution

First application of neural network-represented CASPT2 data to simulate and quantify the reaction dynamics of the Criegee intermediate H$_2$COO with detailed pathway analysis.

Findings

HCO+OH formation is rare (~2%)

Major products are CO$_2$+H$_2$ (~30%) and H$_2$O+CO (~20%)

Over 40% of systems remain reactant within 1 ns

Abstract

The end-to-end dynamics of the smallest energized Criegee intermediate, H$_2$COO, was characterized for vibrational excitation close to and a few kcal/mol above the barrier for hydrogen transfer. From an aggregate of at least 5 $\mu$s of molecular dynamics simulations using a neural network-representation of CASPT2/aug-cc-pVTZ reference data, the branching ratios into molecular products HCO+OH, CO$_2$+H$_2$, or H$_2$O+CO was quantitatively determined. Consistent with earlier calculations and recent experiments, decay into HCO+OH was found to be rare $(\sim 2 \%)$ whereas the other two molecular product channels are accessed with fractions of $\sim 30 \%$ and $\sim 20 \%$, respectively. On the 1 ns time scale, which was the length of an individual MD simulation, more than 40 \% of the systems remain in the reactant state due to partial intramolecular vibrational redistribution (IVR). Formation of CO$_2$+H$_2$ occurs through a bifurcating pathway, one of which passes through formic acid whereas the more probable route connects the di-radical OCH$_2$O with the product through a low-lying transition state. Notably, none of the intermediates along the pathway accumulate and their maximum concentration always remains well below 5 \%. This work demonstrates that atomistic simulations with global reactive machine-learned energy functions provide a quantitative understanding of the chemistry and reaction dynamics for atmospheric reactions in the gas phase.