Modeling halogen bonding with planewave density functional theory: Accuracy and challenges.

Autor: Ang SJ; NUS Graduate School for Integrative Sciences and Engineering, University Hall, Tan Chin Tuan Wing, #04-02, 21 Lower Kent Ridge, Singapore 119077, Singapore., Ser CT; Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore., Wong MW; NUS Graduate School for Integrative Sciences and Engineering, University Hall, Tan Chin Tuan Wing, #04-02, 21 Lower Kent Ridge, Singapore 119077, Singapore.; Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.
Jazyk: angličtina
Zdroj: Journal of computational chemistry [J Comput Chem] 2019 Jul 30; Vol. 40 (20), pp. 1829-1835. Date of Electronic Publication: 2019 Apr 05.
DOI: 10.1002/jcc.25835
Abstrakt: Inspired by the recent interest of halogen bonding (XB) in the solid state, we detail a comprehensive benchmark study of planewave DFT geometry and interaction energy of lone-pair (LP) type and aromatic (AR) type halogen bonded complexes, using PAW and USPP pseudopotentials. For LP-type XB dimers, PBE-PAW generally agrees with PBE/aug-cc-pVQZ(-pp) geometries but significantly overbinds compared to CCSD(T)/aug-cc-pVQZ(-pp). Grimme's D3 dispersion corrections to PBE-PAW gives better agreement to the MP2/cc-pVTZ(-pp) results for AR-type dimers. For interaction energies, PBE-PAW may overbind or underbind for weaker XBs but clearly overbinds for stronger XBs. D3 dispersion corrections exacerbate the overbinding problem for LP-type complexes but significantly improves agreement for AR-type complexes compared to CCSD(T)/CBS. Finally, for periodic XB crystals, planewave PBE methods slightly underestimate the XB lengths by 0.03 to 0.05 Å. © 2019 Wiley Periodicals, Inc.
(© 2019 Wiley Periodicals, Inc.)
Databáze: MEDLINE
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