Open AccessAddressing the System-Size Dependence of the Local Approximation Error in Coupled-Cluster Calculations
Author(s) -
Ahmet Altun,
Soumen Ghosh,
Christoph Riplinger,
Frank Neese,
Giovanni Bistoni
Publication year - 2021
Publication title -
the journal of physical chemistry. a/the journal of physical chemistry. a.
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.756
H-Index - 235
eISSN - 1520-5215
pISSN - 1089-5639
DOI - 10.1021/acs.jpca.1c09106
Subject(s) - extrapolation , approximation error , coupled cluster , limit (mathematics) , cluster (spacecraft) , benchmark (surveying) , physics , space (punctuation) , range (aeronautics) , statistical physics , mathematics , quantum mechanics , statistics , mathematical analysis , molecule , materials science , computer science , geodesy , composite material , programming language , geography , operating system
Over the last two decades, the local approximation has been successfully used to extend the range of applicability of the "gold standard" singles and doubles coupled-cluster method with perturbative triples CCSD(T) to systems with hundreds of atoms. The local approximation error grows in absolute value with the increasing system size, i.e., by increasing the number of electron pairs in the system. In this study, we demonstrate that the recently introduced two-point extrapolation scheme for approaching the complete pair natural orbital (PNOs) space limit in domain-based pair natural orbital CCSD(T) calculations drastically reduces the dependence of the error on the system size, thus opening up unprecedented opportunities for the calculation of benchmark quality relative energies for large systems.