Geometry meta-optimization.

Recent work has demonstrated the promise of using machine-learned surrogates, in particular, Gaussian process (GP) surrogates, in reducing the number of electronic structure calculations (ESCs) needed to perform surrogate model based (SMB) geometry optimization. In this paper, we study geometry meta-optimization with GP surrogates where a SMB optimizer additionally learns from its past "experience" performing geometry optimization. To validate this idea, we start with the simplest setting where a geometry meta-optimizer learns from previous optimizations of the same molecule with different initial-guess geometries. We give empirical evidence that geometry meta-optimization with GP surrogates is effective and requires less tuning compared to SMB optimization with GP surrogates on the ANI-1 dataset of off-equilibrium initial structures of small organic molecules. Unlike SMB optimization where a surrogate should be immediately useful for optimizing a given geometry, a surrogate in geometry meta-optimization has more flexibility because it can distribute its ESC savings across a set of geometries. Indeed, we find that GP surrogates that preserve rotational invariance provide increased marginal ESC savings across geometries. As a more stringent test, we also apply geometry meta-optimization to conformational search on a hand-constructed dataset of hydrocarbons and alcohols. We observe that while SMB optimization and geometry meta-optimization do save on ESCs, they also tend to miss higher energy conformers compared to standard geometry optimization. We believe that further research into characterizing the divergence between GP surrogates and potential energy surfaces is critical not only for advancing geometry meta-optimization but also for exploring the potential of machine-learned surrogates in geometry optimization in general.

Dual-Level Training of Gaussian Processes with Physically Inspired Priors for Geometry Optimizations.

Gaussian process (GP) regression has been recently developed as an effective method in molecular geometry optimization. The prior mean function is one of the crucial parts of the GP. We design and validate two types of physically inspired prior mean functions: force-field-based priors and posterior-type priors. In this work, we implement a dual-level training (DLT) optimizer for the posterior-type priors. The DLT optimizers can be considered as a class of optimization algorithms that belong to the delta-machine learning paradigm but with several major differences compared to the previously proposed algorithms in the same paradigm. In the first level of the DLT, we incorporate the classical mechanical descriptions of the equilibrium geometries into the prior function, which enhances the performance of the GP optimizer as compared to the one using a constant (or zero) prior. In the second level, we utilize the surrogate potential energy surfaces (PESs), which incorporate the physics learned in the first-level training, as the prior function to refine the model performance further. We find that the force-field-based priors and posterior-type priors reduce the overall optimization steps by a factor of 2-3 when compared to the limited-memory Broyden-Fletcher-Goldfarb-Shanno (L-BFGS) optimizer as well as the constant-prior GP optimizer proposed in previous works. We also demonstrate the potential of recovering the real PESs with GP with a force-field prior. This work shows the importance of including domain knowledge as an ingredient in the GP, which offers a potentially robust learning model for molecular geometry optimization and for exploring molecular PESs.