A diagrammatic approach for automatically deriving analytical gradients of tensor hyper-contracted electronic structure methods

We introduce a diagrammatic approach to facilitate the automatic derivation of analytical nuclear gradients for tensor hyper-contraction (THC) based electronic structure methods. The automatically derived gradients are guaranteed to have the same scaling in terms of both operation count and memory footprint as the underlying energy calculations, and the computation of a gradient is roughly three times as costly as the underlying energy. The new diagrammatic approach enables the first cubic scaling implementation of nuclear derivatives for THC tensors fitted in molecular orbital basis (MO-THC). Furthermore, application of this new approach to THC-MP2 analytical gradients leads to an implementation, which is at least four times faster than the previously reported, manually derived implementation. Finally, we apply the new approach to the 14 tensor contraction patterns appearing in the supporting subspace formulation of multireference perturbation theory, laying the foundation for developments of analytical nuclear gradients and nonadiabatic coupling vectors for multi-state CASPT2.

Automated summary

The new diagrammatic approach allows for automatic derivation of analytical nuclear gradients for THC methods, ensuring performance comparable to energy calculations with roughly three times the cost. Its application to THC-MP2 and multi-reference perturbation theory leads to more efficient computations and developments in analytical nuclear gradients.