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Toward First-Principles-Level Polarization Energies in Force Fields: A Gaussian Basis for the Atom-Condensed Kohn-Sham Method

Gütlein, P; Lang, L; Reuter, K; Blumberger, J; Oberhofer, H; (2019) Toward First-Principles-Level Polarization Energies in Force Fields: A Gaussian Basis for the Atom-Condensed Kohn-Sham Method. Journal of Chemical Theory and Computation , 15 (8) pp. 4516-4525. 10.1021/acs.jctc.9b00415. Green open access

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Abstract

The last 20 years of force field development have shown that even well parametrized classical models need to at least approximate the dielectric response of molecular systems-based, e.g., on atomic polarizabilities-in order to correctly render their structural and dynamic properties. Yet, despite great advances most approaches tend to be based on ad hoc assumptions and often insufficiently capture the dielectric response of the system to external perturbations, such as, e.g., charge carriers in semiconducting materials. A possible remedy was recently introduced with the atom-condensed Kohn-Sham density-functional theory approximated to second order (ACKS2), which is fully derived from first principles. Unfortunately, specifically its reliance on first-principles derived parameters so far precluded the widespread adoption of ACKS2. Opening up ACKS2 for general use, we here present a reformulation of the method in terms of Gaussian basis functions, which allows us to determine many of the ACKS2 parameters analytically. Two sets of parameters depending on exchange-correlation interactions are still calculated numerically, but we show that they could be straightforwardly parametrized owing to the smoothness of the new basis. Our approach exhibits three crucial benefits for future applications in force fields: i) efficiency, ii) accuracy, and iii) transferability. We numerically validate our Gaussian augmented ACKS2 model for a set of small hydrocarbons which shows a very good agreement with density-functional theory reference calculations. To further demonstrate the method's accuracy and transferability for realistic systems, we calculate polarization responses and energies of anthracene and tetracene, two major building blocks in organic semiconductors.

Type: Article
Title: Toward First-Principles-Level Polarization Energies in Force Fields: A Gaussian Basis for the Atom-Condensed Kohn-Sham Method
Location: United States
Open access status: An open access version is available from UCL Discovery
DOI: 10.1021/acs.jctc.9b00415
Publisher version: https://doi.org/10.1021/acs.jctc.9b00415
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.
UCL classification: UCL
UCL > Provost and Vice Provost Offices
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy
URI: https://discovery.ucl.ac.uk/id/eprint/10079925
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