Nicolas Grimblat,Gabriel Klassen,Guido Falk von Rudorff
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Data-Driven Complete Basis Set Limit Estimates from a Minimal Auxiliary Basis
Quantum chemistry calculations are often performed using atom-centered basis sets, which are chosen to balance accuracy and cost. While they are systematically improvable, the total energy converges slowly with basis set size toward the complete basis set (CBS) limit. Common extrapolation methods require several intermediate-quality calculations to afford an estimate of the CBS energy. We propose a minimal complementary auxiliary basis set (CABS) baseline to estimate the CBS energy from a single quantum chemistry calculation in a minimal basis set via kernel ridge regression (KRR), which is more efficient than both direct and Δ-machine learning and 40× faster than triple-ζ single-point calculations. The spatial and alchemical gradients from minimal basis and minimal CABS are more accurate than double-ζ (DZ) calculations. We show that KRR on standard molecular representations can be improved by approximating atom-wise local kernels using Chebyshev polynomials, which allows us to train KRR models 10×–50× times faster on moderate compute resources, thereby enabling a data-driven approach toward the mean-field CBS, combining physical baselines capturing leading-order effects with data-efficient machine learning models.
期刊介绍:
The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.