Are dispersion corrections accurate outside equilibrium? A case study on benzene

Gould, T, Johnson, E and Abbas, S 2018, 'Are dispersion corrections accurate outside equilibrium? A case study on benzene', Beilstein Journal of Organic Chemistry, vol. 14, pp. 1181-1191.


Document type: Journal Article
Collection: Journal Articles

Title Are dispersion corrections accurate outside equilibrium? A case study on benzene
Author(s) Gould, T
Johnson, E
Abbas, S
Year 2018
Journal name Beilstein Journal of Organic Chemistry
Volume number 14
Start page 1181
End page 1191
Total pages 11
Publisher Beilstein - Institut zur Foerderung der Chemischen Wissenschaften
Abstract Modern approaches to modelling dispersion forces are becoming increasingly accurate, and can predict accurate binding distances and energies. However, it is possible that these successes reflect a fortuitous cancellation of errors at equilibrium. Thus, in this work we investigate whether a selection of modern dispersion methods agree with benchmark calculations across several potential-energy curves of the benzene dimer to determine if they are capable of describing forces and energies outside equilibrium. We find the exchange-hole dipole moment (XDM) model describes most cases with the highest overall agreement with reference data for energies and forces, with many-body dispersion (MBD) and its fractionally ionic (FI) variant performing essentially as well. Popular approaches, such as Grimme-D and van der Waals density functional approximations (vdW-DFAs) underperform on our tests. The meta-GGA M06-L is surprisingly good for a method without explicit dispersion corrections. Some problems with SCAN+rVV10 are uncovered and briefly discussed.
Subject Condensed Matter Modelling and Density Functional Theory
Electronic and Magnetic Properties of Condensed Matter; Superconductivity
Quantum Chemistry
Keyword(s) Benzene
DFT
Dispersion
Van der Waals
DOI - identifier 10.3762/bjoc.14.99
Copyright notice © 2018 Gould et al.
ISSN 1860-5397
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