Toward universal excited-state machine-learned potentials: a local excitation Hamiltonian for size consistency and transferability

원문 초록

Universal machine-learned interatomic potentials could make excited-state simulations across chemical space routine, but excitation energies, unlike ground-state energies, are not sums of atomic contributions. The excited states of noninteracting molecules are the union of their states, which pooled multistate readouts reproduce at best for the lowest state. We introduce LEH-MACE, whose excitation energies are the eigenvalues of a local excitation Hamiltonian assembled from atom-centred blocks, so this union holds exactly. We generated TD-DFT energies and forces for about 300,000 equilibrium, thermal, and excited-state geometries of over 100,000 molecules. LEH-MACE's advantage over direct readouts grew with the distance from the training data and was largest above $S_1$, with about half their $S_2$ and $S_3$ errors for long conjugated oligomers. For molecule pairs, only LEH-MACE kept its single-molecule accuracy, while a softmin readout remained superior for $S_1$ dynamics of larger chromophores. Exact size consistency is thus one step toward such potentials.