Issue 32, 2024

Extension of the D3 and D4 London dispersion corrections to the full actinides series

Abstract

Efficient dispersion corrections are an indispensable component of modern density functional theory, semi-empirical quantum mechanical, and even force field methods. In this work, we extend the well established D3 and D4 London dispersion corrections to the full actinides series, francium, and radium. To keep consistency with the existing versions, the original parameterization strategy of the D4 model was only slightly modified. This includes improved reference Hirshfeld atomic partial charges at the ωB97M-V/ma-def-TZVP level to fit the required electronegativity equilibration charge (EEQ) model. In this context, we developed a new actinide data set called AcQM, which covers the most common molecular actinide compound space. Furthermore, the efficient calculation of dynamic polarizabilities that are needed to construct CAB6 dispersion coefficients was implemented into the ORCA program package. The extended models are assessed for the computation of dissociation curves of actinide atoms and ions, geometry optimizations of crystal structure cutouts, gas-phase structures of small uranium compounds, and an example extracted from a small actinide complex protein assembly. We found that the novel parameterizations perform on par with the computationally more demanding density-dependent VV10 dispersion correction. With the presented extension, the excellent cost-accuracy ratio of the D3 and D4 models can now be utilized in various fields of computational actinide chemistry and, e.g., in efficient composite DFT methods such as r2SCAN-3c. They are implemented in our freely available standalone codes (dftd4, s-dftd3) and the D4 version will be also available in the upcoming ORCA 6.0 program package.

Graphical abstract: Extension of the D3 and D4 London dispersion corrections to the full actinides series

Supplementary files

Article information

Article type
Paper
Submitted
13 Apr. 2024
Accepted
15 Jūl. 2024
First published
17 Jūl. 2024
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2024,26, 21379-21394

Extension of the D3 and D4 London dispersion corrections to the full actinides series

L. Wittmann, I. Gordiy, M. Friede, B. Helmich-Paris, S. Grimme, A. Hansen and M. Bursch, Phys. Chem. Chem. Phys., 2024, 26, 21379 DOI: 10.1039/D4CP01514B

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