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

Autor: Ang, Shi Jun, Ser, Cher Tian, Wong, Ming Wah
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Zdroj: Journal of Computational Chemistry; 7/30/2019, Vol. 40 Issue 20, p1829-1835, 7p
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. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index
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