Shaw, R.A. orcid.org/0000-0002-9977-0835 and Hill, J.G. orcid.org/0000-0002-6457-5837 (2019) A linear-scaling method for noncovalent interactions : an efficient combination of absolutely localized molecular orbitals and a local random phase approximation approach. Journal of Chemical Theory and Computation, 15 (10). pp. 5352-5369. ISSN 1549-9618
Abstract
A novel method for the accurate and efficient calculation of interaction energies in weakly bound complexes composed of a large number of molecules is presented. The new ALMO+RPAd method circumvents the prohibitive scaling of coupled cluster singles and doubles while still providing similar accuracy across a diverse range of weakly bound chemical systems. Linear-scaling procedures for the Fock build are given utilizing absolutely localized molecular orbitals (ALMOs), resulting in the a priori exclusion of basis set superposition errors. A bespoke data structure and algorithm using density fitting are described, leading to linear scaling for the storage and computation of the two-electron integrals. Electron correlation is included through a new, linear-scaling pairwise local random phase approximation approach, including exchange interactions, and decomposed into purely dispersive excitations (RPAxd). Collectively, these allow meaningful decomposition of the interaction energy into physically distinct contributions: electrostatic, polarization, charge transfer, and dispersion. Comparison with symmetry-adapted perturbation theory shows good qualitative agreement. Tests on various dimers and the S66 benchmark set demonstrate results within 0.5 kcal mol–1 of coupled cluster singles and doubles results. On a large cluster of water molecules, we achieve calculations involving over 3500 orbital and 12,000 auxiliary basis functions in under 10 min on a single CPU core.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2019 American Chemical Society. This is an open access article published under a Creative Commons Attribution (https://creativecommons.org/licenses/by/4.0/) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 13 Sep 2019 13:24 |
Last Modified: | 25 Nov 2020 14:13 |
Status: | Published |
Publisher: | American Chemical Society (ACS) |
Refereed: | Yes |
Identification Number: | 10.1021/acs.jctc.9b00615 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:150728 |