Machine Learning Assisted Selective Configuration Interaction for Accurate Ground and Excited State Calculations

In this work, we introduce a perturbative Selective Configuration Interaction (SCI) approach guided by a binary machine-learning classifier. The method leverages a lightweight feedforward neural network (FNN), purposefully designed for fast and efficient training. Within this framework, we show that our model attains the accuracy of the state-of-the-art SCI method CIPSI (Configuration Interaction using a Perturbative Selection done Iteratively). Across all tested configuration-space sizes, our approach reliably identifies the most important Slater determinants using a binary cross-entropy metric, achieving FCI/CASCI-level accuracy within 10 –4 Hartree for both ground and excited states. Finally, the method remains robust for strained geometries and conformational changes, successfully classifying Slater determinants across multiple points of potential energy curves and surfaces. This capability opens the door to new regression-based strategies for molecular electronic structure and the construction of machine-learning-driven potential energy surfaces.