Machine Learning-Assisted Mixed Quantum-Classical Dynamics without Explicit Nonadiabatic Coupling: Application to the...

We have devised a hybrid quantum-classical scheme utilizing machine-learned potential energy surfaces (PES), which circumvents the need for explicit computation of nonadiabatic coupling elements. The quantities necessary to account for the nonadiabatic effects are directly obtained from the PESs. The simulation of dynamics is based on the fewest-switches surface-hopping method. We applied this scheme to model the photodissociation of both N-O and O-O bonds in a conformer of peroxynitric acid (HO₂NO₂). Adiabatic PES data for the six lowest states of this molecule were computed at the CASSCF level for various nuclear configurations. These served as the training data for the machine-learning models for the PESs. The dynamics simulation was initiated on the lowest optically bright singlet excited state (S₄) and propagated along the two Jacobi coordinates $$ and $$ while accounting for the nonadiabatic effects through transitions between PESs. Our analysis revealed that there is a very high chance of dissociation of the N-O bond leading to the HO₂ and NO₂ fragments.