A particle view of many-body electronic structure with neural network wavefunction

Abstract

In the study of electronic structure, the wavefunction view dominates the current research landscape and forms the theoretical foundation of modern quantum mechanics. In contrast, Valence Bond (VB) theory represents chemical bonds as shared electron-pairs and can provide an intuitive, particle-based insight into chemical bonding. In this work, using a newly developed Periodic Dynamic Voronoi Metropolis Sampling (PDVMS) method, we project classical many-body electronic configurations from the neural network wavefunction, and apply VB theory to construct a complementary particle-view paradigm. The powerful neural network wavefunction can achieve near-exact ab initio solutions for the ground state of both molecular and solid systems. It allows us to definitively characterize the ground state of benzene by reassessing the competition between its two VB structures. Extending PDVMS to solids for the first time, we also predict a spin-staggered VB structure in graphene, which explains emergent magnetic properties in graphene-based nanostructures. Furthermore, this particle view provides insight into the optimization process of the neural network wavefunction itself. Our work thus introduces a novel framework for analyzing many-body electronic structure in molecules and solids, opening new avenues for investigating this complex problem and its associated exotic phenomena.