Accurate and Efficient Open-Source Implementation of Domain-Based Local Pair Natural Orbital (DLPNO) Coupled-Cluster Theory Using a t1-Transformed Hamiltonian

11 June 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Here, 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).


Coupled-Cluster Theory
Modeling Large Molecules
Quantum Chemistry Software

Supplementary materials

Supplementary Information
Includes additional tables and figures, detailed data for each computation presented in the paper, as well as relevant xyz molecular geometries


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