Excited Pfaffians: Generalized Neural Wave Functions Across Structure and State

摘要

Neural-network wave functions in Variational Monte Carlo (VMC) have achieved great success in accurately representing both ground and excited states. However, achieving sufficient numerical accuracy of state overlaps requires growing the number of Monte Carlo samples, and consequently computational cost, with the number of states. We present a nearly constant sample size approach named Multi-State Importance Sampling (MSIS), which leverages all states' samples to estimate any pairwise overlap. To efficiently evaluate all states for all samples, we introduce Excited Pfaffians. Inspired by Hartree-Fock, this architecture represents many states within a single neural network. Excited Pfaffians also serve as generalized wave functions, allowing a single model to represent multi-state potential energy surfaces. On the carbon dimer, we match the $\mathcal{O}(N_s^4)$-scaling natural excited states while training $>200\times$ faster and modeling 50% more states. Our favorable scaling enables us to be the first to use neural networks to find all distinct energy levels of the Beryllium atom. Finally, we demonstrate that a single wave function can represent excited states across various molecules.