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Toward transferable interatomic van der Waals interactions without electrons: the role of multipole electrostatics and many-body dispersion

Bereau, Tristan and von Lilienfeld, O. Anatole. (2014) Toward transferable interatomic van der Waals interactions without electrons: the role of multipole electrostatics and many-body dispersion. Journal of Chemical Physics, 141 (3). 034101.

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Official URL: http://edoc.unibas.ch/43356/

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Abstract

We estimate polarizabilities of atoms in molecules without electron density, using a Voronoi tesselation approach instead of conventional density partitioning schemes. The resulting atomic dispersion coefficients are calculated, as well as many-body dispersion effects on intermolecular potential energies. We also estimate contributions from multipole electrostatics and compare them to dispersion. We assess the performance of the resulting intermolecular interaction model from dispersion and electrostatics for more than 1300 neutral and charged, small organic molecular dimers. Applications to water clusters, the benzene crystal, the anti-cancer drug ellipticine-intercalated between two Watson-Crick DNA base pairs, as well as six macro-molecular host-guest complexes highlight the potential of this method and help to identify points of future improvement. The mean absolute error made by the combination of static electrostatics with many-body dispersion reduces at larger distances, while it plateaus for two-body dispersion, in conflict with the common assumption that the simple 1/R(6) correction will yield proper dissociative tails. Overall, the method achieves an accuracy well within conventional molecular force fields while exhibiting a simple parametrization protocol.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Lilienfeld)
UniBasel Contributors:von Lilienfeld, Anatole
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:AIP Publishing
ISSN:0021-9606
e-ISSN:1089-7690
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:24 Apr 2017 09:35
Deposited On:20 Jun 2016 09:38

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