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.

Abstract

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).

Keywords

Coupled-Cluster Theory
Modeling Large Molecules
Quantum Chemistry Software
Linear-scaling

Supplementary materials

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