DLPNO-CCSD(T) scaled methods for the accurate treatment of large supramolecular complexes
© 2017 Wiley Periodicals, Inc.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 38(2017), 21 vom: 05. Juni, Seite 1869-1878 |
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| Weitere Verfasser: | , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2017
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article Research Support, Non-U.S. Gov't DLPNO-CCSD(T) scaled methods ab initio calculations dispersion forces donor-acceptor supramolecular complexes noncovalent interactions |
| Zusammenfassung: | © 2017 Wiley Periodicals, Inc. In this work, we present scaled variants of the DLPNO-CCSD(T) method, dubbed as (LS)DLPNO-CCSD(T) and (NS)DLPNO-CCSD(T), to obtain accurate interaction energies in supramolecular complexes governed by noncovalent interactions. The novel scaled schemes are based on the linear combination of the DLPNO-CCSD(T) correlation energies calculated with the standard (LoosePNO and NormalPNO) and modified (Loose2PNO and Normal2PNO) DLPNO-CCSD(T) accuracy levels. The scaled DLPNO-CCSD(T) variants provide nearly TightPNO accuracy, which is essential for the quantification of weak noncovalent interactions, with a noticeable saving in computational cost. Importantly, the accuracy of the proposed schemes is preserved irrespective of the nature and strength of the supramolecular interaction. The (LS)DLPNO-CCSD(T) and (NS)DLPNO-CCSD(T) protocols have been used to study in depth the role of the CH-π versus π-π interactions in the supramolecular complex formed by the electron-donor truxene-tetrathiafulvalene (truxTTF) and the electron-acceptor hemifullerene (C30 H12 ). (NS)DLPNO-CCSD(T)/CBS calculations clearly reveal the higher stability of staggered (dominated by CH-π interactions) versus bowl-in-bowl (dominated by π-π interactions) arrangements in the truxTTF•C30 H12 heterodimer. Hemifullerene and similar carbon-based buckybowls are therefore expected to self-assemble with donor compounds in a richer way other than the typical concave-convex π-π arrangement found in fullerene-based aggregates. © 2017 Wiley Periodicals, Inc |
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| Beschreibung: | Date Revised 20.11.2019 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.24835 |