Communication: An improved linear scaling perturbative triples correction for the domain based local pair-natural orbital based singles and doubles coupled cluster method [DLPNO-CCSD(T)]
Liakos, Dimitrios G.
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Online Publication Date2018-01-04
Print Publication Date2018-01-07
Permanent link to this recordhttp://hdl.handle.net/10754/626850
MetadataShow full item record
AbstractIn this communication, an improved perturbative triples correction (T) algorithm for domain based local pair-natural orbital singles and doubles coupled cluster (DLPNO-CCSD) theory is reported. In our previous implementation, the semi-canonical approximation was used and linear scaling was achieved for both the DLPNO-CCSD and (T) parts of the calculation. In this work, we refer to this previous method as DLPNO-CCSD(T0) to emphasize the semi-canonical approximation. It is well-established that the DLPNO-CCSD method can predict very accurate absolute and relative energies with respect to the parent canonical CCSD method. However, the (T0) approximation may introduce significant errors in absolute energies as the triples correction grows up in magnitude. In the majority of cases, the relative energies from (T0) are as accurate as the canonical (T) results of themselves. Unfortunately, in rare cases and in particular for small gap systems, the (T0) approximation breaks down and relative energies show large deviations from the parent canonical CCSD(T) results. To address this problem, an iterative (T) algorithm based on the previous DLPNO-CCSD(T0) algorithm has been implemented [abbreviated here as DLPNO-CCSD(T)]. Using triples natural orbitals to represent the virtual spaces for triples amplitudes, storage bottlenecks are avoided. Various carefully designed approximations ease the computational burden such that overall, the increase in the DLPNO-(T) calculation time over DLPNO-(T0) only amounts to a factor of about two (depending on the basis set). Benchmark calculations for the GMTKN30 database show that compared to DLPNO-CCSD(T0), the errors in absolute energies are greatly reduced and relative energies are moderately improved. The particularly problematic case of cumulene chains of increasing lengths is also successfully addressed by DLPNO-CCSD(T).
CitationGuo Y, Riplinger C, Becker U, Liakos DG, Minenkov Y, et al. (2018) Communication: An improved linear scaling perturbative triples correction for the domain based local pair-natural orbital based singles and doubles coupled cluster method [DLPNO-CCSD(T)]. The Journal of Chemical Physics 148: 011101. Available: http://dx.doi.org/10.1063/1.5011798.
SponsorsF.N. and Y.G. gratefully acknowledge financial support by the Max Planck Society and the cluster of excellence (RESOLV, University of Bochum, No. EXC 1069). Y.G. is thankful to Peter Pinski for helpful discussion.
JournalThe Journal of Chemical Physics
- Linear scaling perturbative triples correction approximations for open-shell domain-based local pair natural orbital coupled cluster singles and doubles theory [DLPNO-CCSD(T<sub>0</sub>/T)].
- Authors: Guo Y, Riplinger C, Liakos DG, Becker U, Saitow M, Neese F
- Issue date: 2020 Jan 14
- Natural triple excitations in local coupled cluster calculations with pair natural orbitals.
- Authors: Riplinger C, Sandhoefer B, Hansen A, Neese F
- Issue date: 2013 Oct 7
- Perturbative triples correction for local pair natural orbital based explicitly correlated CCSD(F12*) using Laplace transformation techniques.
- Authors: Schmitz G, Hättig C
- Issue date: 2016 Dec 21
- Is It Possible To Obtain Coupled Cluster Quality Energies at near Density Functional Theory Cost? Domain-Based Local Pair Natural Orbital Coupled Cluster vs Modern Density Functional Theory.
- Authors: Liakos DG, Neese F
- Issue date: 2015 Sep 8
- Scalable Electron Correlation Methods. 5. Parallel Perturbative Triples Correction for Explicitly Correlated Local Coupled Cluster with Pair Natural Orbitals.
- Authors: Ma Q, Werner HJ
- Issue date: 2018 Jan 9