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)]
Type
ArticleAuthors
Guo, YangRiplinger, Christoph
Becker, Ute
Liakos, Dimitrios G.
Minenkov, Yury

Cavallo, Luigi

Neese, Frank
KAUST Department
KAUST Catalysis Center (KCC)Physical Sciences and Engineering (PSE) Division
Chemical Science Program
Date
2018-01-04Online Publication Date
2018-01-04Print Publication Date
2018-01-07Permanent link to this record
http://hdl.handle.net/10754/626850
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Show full item recordAbstract
In 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).Citation
Guo 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.Sponsors
F.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.Publisher
AIP PublishingJournal
The Journal of Chemical PhysicsPubMed ID
29306283Additional Links
http://aip.scitation.org/doi/10.1063/1.5011798ae974a485f413a2113503eed53cd6c53
10.1063/1.5011798
Scopus Count
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