Machine Learning Nonadiabatic Dynamics: Eliminating Phase Freedom of Nonadiabatic Couplings with the State-Interaction State-Averaged Spin-Restricted Ensemble-Referenced Kohn–Sham Approach

Excited-state molecular dynamics (ESMD) simulations near conical intersections (CIs) pose significant challenges when using machine learning potentials (MLPs). Although MLPs have gained recognition for their integration into mixed quantum-classical (MQC) methods, such as trajectory surface hopping (TSH), and their capacity to model correlated electron-nuclear dynamics efficiently, difficulties persist in managing nonadiabatic dynamics. Specifically, singularities at CIs and double-valued coupling elements result in discontinuities that disrupt the smoothness of predictive functions. Partial solutions have been provided by learning diabatic Hamiltonians with phaseless loss functions to these challenges. However, a definitive method for addressing the discontinuities caused by CIs and double-valued coupling elements has yet to be developed. Here, we introduce the phaseless coupling term, Δ², derived from the square of the off-diagonal elements of the diabatic Hamiltonian in the state-interaction state-averaged spin-restricted ensemble-referenced Kohn-Sham (SI-SA-REKS, briefly SSR)(2,2) formalism. This approach improves the stability and accuracy of the MLP model by addressing the issues arising from CI singularities and double-valued coupling functions. We apply this method to the penta-2,4-dieniminium cation (PSB3), demonstrating its effectiveness in improving MLP training for ML-based nonadiabatic dynamics. Our results show that the Δ²-based ML-ESMD method can reproduce ab initio ESMD simulations, underscoring its potential and efficiency for broader applications, particularly in large-scale and long-time scale ESMD simulations.