Efficient implementation of molecular CCSD gradients with Cholesky-decomposed electron repulsion integrals.

We present an efficient implementation of ground and excited state coupled cluster singles and doubles (CCSD) gradients based on Cholesky-decomposed electron repulsion integrals. Cholesky decomposition and density fitting are both inner projection methods, and, thus, similar implementation schemes can be applied for both methods. One well-known advantage of inner projection methods, which we exploit in our implementation, is that one can avoid storing large V3O and V4 arrays by instead considering three-index intermediates. Furthermore, our implementation does not require the formation and storage of Cholesky vector derivatives. The new implementation is shown to perform well, with less than 10% of the time spent calculating the gradients in geometry optimizations. Furthermore, the computational time per optimization cycle is significantly lower compared to other implementations based on an inner projection method. We showcase the capabilities of the implementation by optimizing the geometry of the retinal molecule (C20H28O) at the CCSD/aug-cc-pVDZ level of theory.

Citation

Anna Kristina Schnack-Petersen, Henrik Koch, Sonia Coriani, Eirik F Kjønstad. Efficient implementation of molecular CCSD gradients with Cholesky-decomposed electron repulsion integrals. The Journal of chemical physics. 2022 Jun 28;156(24):244111

PMID: 35778080

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