English

Interpolating many-body wave functions for accelerated molecular dynamics on the near-exact electronic surface

Chemical Physics 2025-04-04 v2 Strongly Correlated Electrons Computational Physics Quantum Physics

Abstract

While there have been many developments in computational probes of both strongly-correlated molecular systems and machine-learning accelerated molecular dynamics, there remains a significant gap in capabilities in simulating accurate non-local electronic structure over timescales on which atoms move. We develop an approach to bridge these fields with a practical interpolation scheme for the correlated many-electron state through the space of atomic configurations, whilst avoiding the exponential complexity of these underlying electronic states. With a small number of accurate correlated wave functions as a training set, we demonstrate provable convergence to near-exact potential energy surfaces for subsequent dynamics with propagation of a valid many-body wave function and inference of its variational energy whilst retaining a mean-field computational scaling. This represents a profoundly different paradigm to the direct interpolation of potential energy surfaces in established machine-learning approaches. We combine this with modern electronic structure approaches to systematically resolve molecular dynamics trajectories and converge thermodynamic quantities with a high-throughput of several million interpolated wave functions with explicit validation of their accuracy from only a few numerically exact quantum chemical calculations. We also highlight the comparison to traditional machine-learned potentials or dynamics on mean-field surfaces.

Keywords

Cite

@article{arxiv.2402.11097,
  title  = {Interpolating many-body wave functions for accelerated molecular dynamics on the near-exact electronic surface},
  author = {Yannic Rath and George H. Booth},
  journal= {arXiv preprint arXiv:2402.11097},
  year   = {2025}
}
R2 v1 2026-06-28T14:51:29.268Z