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Implementation and Validation of Constrained Density Functional Theory Forces in the CP2K Package

Ahart, Christian S; Rosso, Kevin M; Blumberger, Jochen; (2022) Implementation and Validation of Constrained Density Functional Theory Forces in the CP2K Package. Journal of Chemical Theory and Computation 10.1021/acs.jctc.2c00284. (In press). Green open access

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Abstract

Constrained density functional theory (CDFT) is a powerful tool for the prediction of electron transfer parameters in condensed phase simulations at a reasonable computational cost. In this work we present an extension to CDFT in the popular mixed Gaussian/plane wave electronic structure package CP2K, implementing the additional force terms arising from a constraint based on Hirshfeld charge partitioning. This improves upon the existing Becke partitioning scheme, which is prone to give unphysical atomic charges. We verify this implementation for a variety of systems: electron transfer in (H_{2}O)_{2}^{+} in a vacuum, electron tunnelling between oxygen vacancy centers in solid MgO, and electron self-exchange in aqueous Ru^{2+}-Ru^{3+}. We find good agreement with previous plane-wave CDFT results for the same systems, but at a significantly lower computational cost, and we discuss the general reliability of condensed phase CDFT calculations.

Type: Article
Title: Implementation and Validation of Constrained Density Functional Theory Forces in the CP2K Package
Location: United States
Open access status: An open access version is available from UCL Discovery
DOI: 10.1021/acs.jctc.2c00284
Publisher version: https://doi.org/10.1021/acs.jctc.2c00284
Language: English
Additional information: © 2022 The Authors. Published by American Chemical Society under the terms of the Creative Commons Attribution 4.0 International (CC BY 4.0) Licence (https://creativecommons.org/licenses/by/4.0/).
UCL classification: 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
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL
URI: https://discovery.ucl.ac.uk/id/eprint/10150585
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