ct6b01198_si_002.txt (41.33 kB)
Empirical D3 Dispersion as a Replacement for ab Initio Dispersion Terms in Density Functional Theory-Based Symmetry-Adapted Perturbation Theory
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posted on 2017-03-07, 00:00 authored by Robert Sedlak, Jan ŘezáčIn
density functional theory-based symmetry-adapted perturbation
theory (DFT-SAPT) interaction energy calculations, the most demanding
step is the calculation of the London dispersion term. For this bottleneck
to be avoided and DFT-SAPT to be made applicable to larger systems,
the ab initio dispersion terms can be replaced by one calculated empirically
at an almost negligible cost (J. Phys. Chem. A 2011; 115, 11321−11330). We
present an update of this approach that improves accuracy and makes
the method applicable to a wider range of systems. It is based on
Grimme’s D3 dispersion correction for DFT, where the damping
function is changed to one suitable for the calculation of the complete
dispersion energy. The best results have been achieved with the Tang–Toennies
damping function. It has been parametrized on the S66×8 data
set for which we report density fitting DFT-SAPT/aug-cc-pVTZ interaction
energy decomposition. The method has been validated on a diverse set
of noncovalent systems including difficult cases such as very compact
noncovalent complexes of charge-transfer type. The root-mean-square
errors in the complete test set are 0.73 and 0.42 kcal mol–1 when charge-transfer complexes are excluded. The proposed empirical
dispersion terms can also be used outside the DFT-SAPT framework,
e.g., for the estimation of the amount of dispersion in a calculation
where only the total interaction energy is known.
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report densitydispersion termsroot-mean-square errorsab Initio Dispersion Termstheory-based symmetry-adapted perturbation theoryLondon dispersion termEmpirical D 3 Dispersionnoncovalent complexescharge-transfer typecharge-transfer complexesDensity Functional Theory-Based Symmetry-Adapted Perturbation Theoryinteraction energy calculationsinteraction energynoncovalent systemsdispersion energyab initio dispersion termsDFT-SAPT framework
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