Machine Learning Electronic Structure Methods Based On The One-Electron Reduced Density Matrix

TL;DR

This paper introduces machine learning surrogate models for electronic structure calculations based on the one-electron reduced density matrix, enabling fast, accurate predictions of molecular properties and dynamics without traditional computational costs.

Contribution

It presents a novel approach using machine learning to generate surrogate electronic structure methods based on the one-electron reduced density matrix, applicable to various quantum chemistry theories.

Findings

Surrogate models accurately reproduce standard quantum chemistry results.

Models can predict energies, molecular orbitals, and spectra efficiently.

Enables molecular dynamics and spectral simulations without expensive algorithms.

Abstract

The theorems of density functional theory (DFT) and reduced density matrix functional theory (RDMFT) establish a bijective map between the external potential of a many-body system and its electron density or one-particle reduced density matrix. Building on this foundation, we show that machine learning can be used to generate surrogate electronic structure methods. In particular, we generate surrogates of local and hybrid DFT as well as Hartree-Fock and full configuration interaction theories for systems ranging from small molecules such as water to more complex compounds like propanol and benzene. The surrogate models use the one-electron reduced density matrix as the central quantity to be learned. From the predicted density matrices, we show that either standard quantum chemistry or a second machine-learning model can be used to compute molecular observables, energies, and atomic forces. We show that the surrogate models can generate essentially anything that a standard electronic structure method can, ranging from band gaps and Kohn-Sham orbitals to energy-conserving ab-initio molecular dynamics simulations and IR spectra, which account anharmonicity and thermal effects, without the need of computationally expensive algorithms such as self-consistent field theory. The algorithms developed here are packaged in an efficient and easy to use Python code, QMLearn, accessible by the broader community on popular platforms.