Near-linear Scaling in DMRG-based Tailored Coupled Clusters: An Implementation of DLPNO-TCCSD and DLPNO-TCCSD(T)

Abstract

We present a new implementation of DMRG-based tailored coupled clusters method (TCCSD), which employs the domain-based local pair natural orbital approach (DLPNO-TCCSD). Compared to the previous LPNO version of the method, the new implementation is more accurate, offers more favorable scaling and provides more consistent behavior across the variety of systems. On top of the singles and doubles, we include the perturbative triples correction (T), which is able to retrieve even more dynamic correlation. The methods were tested on three systems: tetramethyleneethane, oxo-Mn(Salen) and Iron(II)-porphyrin model. The first two were revisited to assess the performance with respect to LPNO-TCCSD. For oxo-Mn(Salen), we retrieved between 99.8-99.9% of the total canonical correlation energy which is the improvement of 0.2% over the LPNO version in less than 63% of the total LPNO runtime. Similar results were obtained for Iron(II)-porphyrin. When the perturbative triples correction was employed, irrespective of the active space size or system, the obtained energy differences between two spin states were within the chemical accuracy of 1 kcal/mol using the default DLPNO settings.

Updated version: 15 pages. arXiv admin note: text overlap with arXiv:1905.06833

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• Complete Active Space Iterative Coupled Cluster Theory
• Coupled cluster method tailored with quantum computing
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• Three Lagrangians for the complete-active space coupled-cluster method
• DMRG-tailored coupled cluster method in the 4c-relativistic domain: General implementation and application to the NUHFI and NUF${}_3$ molecules