Issue 34, 2019

New scaling relations to compute atom-in-material polarizabilities and dispersion coefficients: part 1. Theory and accuracy

Abstract

Polarizabilities and London dispersion forces are important to many chemical processes. Force fields for classical atomistic simulations can be constructed using atom-in-material polarizabilities and Cn (n = 6, 8, 9, 10…) dispersion coefficients. This article addresses the key question of how to efficiently assign these parameters to constituent atoms in a material so that properties of the whole material are better reproduced. We develop a new set of scaling laws and computational algorithms (called MCLF) to do this in an accurate and computationally efficient manner across diverse material types. We introduce a conduction limit upper bound and m-scaling to describe the different behaviors of surface and buried atoms. We validate MCLF by comparing results to high-level benchmarks for isolated neutral and charged atoms, diverse diatomic molecules, various polyatomic molecules (e.g., polyacenes, fullerenes, and small organic and inorganic molecules), and dense solids (including metallic, covalent, and ionic). We also present results for the HIV reverse transcriptase enzyme complexed with an inhibitor molecule. MCLF provides the non-directionally screened polarizabilities required to construct force fields, the directionally-screened static polarizability tensor components and eigenvalues, and environmentally screened C6 coefficients. Overall, MCLF has improved accuracy compared to the TS-SCS method. For TS-SCS, we compared charge partitioning methods and show DDEC6 partitioning yields more accurate results than Hirshfeld partitioning. MCLF also gives approximations for C8, C9, and C10 dispersion coefficients and quantum Drude oscillator parameters. This method should find widespread applications to parameterize classical force fields and density functional theory (DFT) + dispersion methods.

Graphical abstract: New scaling relations to compute atom-in-material polarizabilities and dispersion coefficients: part 1. Theory and accuracy

Supplementary files

Article information

Article type
Paper
Submitted
23 apr. 2019
Accepted
03 jún. 2019
First published
19 jún. 2019
This article is Open Access
Creative Commons BY license

RSC Adv., 2019,9, 19297-19324

New scaling relations to compute atom-in-material polarizabilities and dispersion coefficients: part 1. Theory and accuracy

T. A. Manz, T. Chen, D. J. Cole, N. G. Limas and B. Fiszbein, RSC Adv., 2019, 9, 19297 DOI: 10.1039/C9RA03003D

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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