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. 2025 Mar 11;21(5):2386-2401.
doi: 10.1021/acs.jctc.4c01716. Epub 2025 Feb 21.

Linear-Scaling Local Natural Orbital-Based Full Triples Treatment in Coupled-Cluster Theory

Andy Jiang  1 , Henry F Schaefer 3rd  1 , Justin M Turney  1
Affiliations

Linear-Scaling Local Natural Orbital-Based Full Triples Treatment in Coupled-Cluster Theory

Andy Jiang et al. J Chem Theory Comput. .

Abstract

We present an efficient, asymptotically linear-scaling implementation of the canonically O(N8) coupled-cluster method with singles, doubles, and full triples excitations (CCSDT) method. We apply the domain-based local pair natural orbital (DLPNO) approach for computing CCSDT amplitudes. Our method, called DLPNO-CCSDT, uses the converged coupled-cluster amplitudes from a preceding DLPNO-CCSD(T) computation as a starting point for the solution of the CCSDT equations in the local natural orbital basis. To simplify the working equations, we t1-dress our two-electron integrals and Fock matrices, allowing our equations to take on the form of CCDT. With appropriate parameters, our method can recover more than 99.99% of the total canonical CCSDT correlation energy. In addition, we demonstrate that our method consistently yields sub-kJ mol-1 errors in relative energies when compared to canonical CCSDT, and, likewise, when computing the difference between CCSDT and CCSD(T). Finally, to highlight the low scaling of our algorithm, we present timings on linear alkanes (up to 30 carbons and 730 basis functions) and water clusters (up to 131 water molecules and 3144 basis functions).

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Convergence of the DLPNO–CCSD(T)/T correlation energy for benzene/cc-pVDZ with respect to the TNO tolerance for strong/weak triples. Dotted red lines represent target accuracy (less than 0.01% error in the correlation energy recovered).
Figure 2
Figure 2
Convergence of the DLPNO–CCSD(T)/T correlation energy for HCNO/cc-pVTZ with respect to the TNO tolerance for strong/weak triples. Dotted red lines represent target accuracy (less than 0.01% error in the correlation energy recovered).
Figure 3
Figure 3
Representation of the geometries for the pericyclic reactions referenced in Table 2.
Figure 4
Figure 4
Representation of the geometries of the pericyclic barrier heights referenced in Table 3.
Figure 5
Figure 5
Linear alkane wall time per iteration for DLPNO–CCSDT. System sizes range from 1–30 carbons for the cc-pVDZ basis set, and 1–12 carbons for the cc-pVTZ basis set.
Figure 6
Figure 6
Water cluster wall time per iteration for DLPNO–CCSDT. System sizes range from 4–131 waters in cc-pVDZ, and 4–49 waters in cc-pVTZ.
See this image and copyright information in PMC

References

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