Machine Learning-Assisted Excited State Molecular Dynamics with the State-Interaction State-Averaged Spin-Restricted Ensemble-Referenced Kohn–Sham Approach

We present a machine learning-assisted excited state molecular dynamics (ML-ESMD) based on the ensemble density functional theory framework. Since we represent a diabatic Hamiltonian in terms of generalized valence bond ansatz within the state-interaction state-averaged spin-restricted ensemble-referenced Kohn–Sham (SI-SA-REKS) method, we can avoid singularities near conical intersections, which are crucial in excited state molecular dynamics simulations. We train the diabatic Hamiltonian elements and their analytical gradients with the SchNet architecture to construct machine learning models, while the phase freedom of off-diagonal elements of the Hamiltonian is cured by introducing the phase-less loss function. Our machine learning models show reasonable accuracy with mean absolute errors of ∼0.1 kcal/mol and ∼0.5 kcal/mol/Å for the diabatic Hamiltonian elements and their gradients, respectively, for penta-2,4-dieniminium cation. Moreover, by exploiting the diabatic representation, our models can predict correct conical intersection structures and their topologies. In addition, our ML-ESMD simulations give almost identical result with a direct dynamics at the same level of theory.