skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Approaching the complete basis set limit of CCSD(T) for large systems by the third-order incremental dual-basis set zero-buffer F12 method

Abstract

The third-order incremental dual-basis set zero-buffer approach was combined with CCSD(T)-F12x (x = a, b) theory to develop a new approach, i.e., the inc3-db-B0-CCSD(T)-F12 method, which can be applied as a black-box procedure to efficiently obtain the near complete basis set (CBS) limit of the CCSD(T) energies also for large systems. We tested this method for several cases of different chemical nature: four complexes taken from the standard benchmark sets S66 and X40, the energy difference between isomers of water hexamer and the rotation barrier of biphenyl. The results show that our method has an error relative to the best estimation of CBS energy of only 0.2 kcal/mol or less. By parallelization, our method can accomplish the CCSD(T)-F12 calculations of about 60 correlated electrons and 800 basis functions in only several days, which by standard implementation are impossible for ordinary hardware. We conclude that the inc3-db-B0-CCSD(T)-F12a/AVTZ method, which is of CCSD(T)/AV5Z quality, is close to the limit of accuracy that one can achieve for large systems currently.

Authors:
;  [1]
  1. Department of Chemistry, University of Cologne, Cologne 50939 (Germany)
Publication Date:
OSTI Identifier:
22255200
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 140; Journal Issue: 4; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; BIPHENYL; BUFFERS; ELECTRONS; ISOMERS

Citation Formats

Zhang, Jun, and Dolg, Michael. Approaching the complete basis set limit of CCSD(T) for large systems by the third-order incremental dual-basis set zero-buffer F12 method. United States: N. p., 2014. Web. doi:10.1063/1.4862826.
Zhang, Jun, & Dolg, Michael. Approaching the complete basis set limit of CCSD(T) for large systems by the third-order incremental dual-basis set zero-buffer F12 method. United States. https://doi.org/10.1063/1.4862826
Zhang, Jun, and Dolg, Michael. 2014. "Approaching the complete basis set limit of CCSD(T) for large systems by the third-order incremental dual-basis set zero-buffer F12 method". United States. https://doi.org/10.1063/1.4862826.
@article{osti_22255200,
title = {Approaching the complete basis set limit of CCSD(T) for large systems by the third-order incremental dual-basis set zero-buffer F12 method},
author = {Zhang, Jun and Dolg, Michael},
abstractNote = {The third-order incremental dual-basis set zero-buffer approach was combined with CCSD(T)-F12x (x = a, b) theory to develop a new approach, i.e., the inc3-db-B0-CCSD(T)-F12 method, which can be applied as a black-box procedure to efficiently obtain the near complete basis set (CBS) limit of the CCSD(T) energies also for large systems. We tested this method for several cases of different chemical nature: four complexes taken from the standard benchmark sets S66 and X40, the energy difference between isomers of water hexamer and the rotation barrier of biphenyl. The results show that our method has an error relative to the best estimation of CBS energy of only 0.2 kcal/mol or less. By parallelization, our method can accomplish the CCSD(T)-F12 calculations of about 60 correlated electrons and 800 basis functions in only several days, which by standard implementation are impossible for ordinary hardware. We conclude that the inc3-db-B0-CCSD(T)-F12a/AVTZ method, which is of CCSD(T)/AV5Z quality, is close to the limit of accuracy that one can achieve for large systems currently.},
doi = {10.1063/1.4862826},
url = {https://www.osti.gov/biblio/22255200}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 4,
volume = 140,
place = {United States},
year = {Tue Jan 28 00:00:00 EST 2014},
month = {Tue Jan 28 00:00:00 EST 2014}
}