Accurate and efficient open-source implementation of domain-based local pair natural orbital (DLPNO) coupled-cluster theory using a t1-transformed Hamiltonian

Andy Jiang; Zachary L Glick; David Poole; Justin M Turney; C David Sherrill; Henry F Schaefer 3rd

doi:10.1063/5.0219963

Accurate and efficient open-source implementation of domain-based local pair natural orbital (DLPNO) coupled-cluster theory using a t1-transformed Hamiltonian

J Chem Phys. 2024 Aug 28;161(8):082502. doi: 10.1063/5.0219963.

Authors

Andy Jiang¹, Zachary L Glick², David Poole², Justin M Turney¹, C David Sherrill², Henry F Schaefer 3rd¹

Affiliations

¹ Center for Computational Quantum Chemistry, Department of Chemistry, University of Georgia, Athens, Georgia 30602, USA.
² Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, School of Computational Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.

PMID: 39171707
DOI: 10.1063/5.0219963

Abstract

We present an efficient, open-source formulation for coupled-cluster theory through perturbative triples with domain-based local pair natural orbitals [DLPNO-CCSD(T)]. Similar to the implementation of the DLPNO-CCSD(T) method found in the ORCA package, the most expensive integral generation and contraction steps associated with the CCSD(T) method are linear-scaling. In this work, we show that the t1-transformed Hamiltonian allows for a less complex algorithm when evaluating the local CCSD(T) energy without compromising efficiency or accuracy. Our algorithm yields sub-kJ mol-1 deviations for relative energies when compared with canonical CCSD(T), with typical errors being on the order of 0.1 kcal mol-1, using our TightPNO parameters. We extensively tested and optimized our algorithm and parameters for non-covalent interactions, which have been the most difficult interaction to model for orbital (PNO)-based methods historically. To highlight the capabilities of our code, we tested it on large water clusters, as well as insulin (787 atoms).