Geometry Optimization in Internal Coordinates Based on Gaussian Process Regression: Comparison of Two Approaches

Geometry optimization based on Gaussian process regression (GPR) was extended to internal coordinates. We used delocalized internal coordinates composed of distances and several types of angles and compared two methods of including them. In both cases, the GPR surrogate surface is trained on geometries in internal coordinates. In one case, it predicts the gradient in Cartesian coordinates and in the other, in internal coordinates. We tested both methods on a set of 30 small molecules and one larger Rh complex taken from the study of a catalytic mechanism. The former method is slightly more efficient, while the latter method is somewhat more robust. Both methods reduce the number of required optimization steps compared to GPR in Cartesian coordinates or the standard L-BFGS optimizer. We found it advantageous to use automatically adjusted hyperparameters to optimize them.