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

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 (H₂O)₂⁺ in a vacuum, electron tunnelling between oxygen vacancy centers in solid MgO, and electron self-exchange in aqueous Ru²⁺-Ru³⁺. 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.

SUBMITTER: Ahart CS

PROVIDER: S-EPMC9281399 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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

Ahart Christian S CS Rosso Kevin M KM Blumberger Jochen J

Journal of chemical theory and computation 20220614 7

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 unphysica ...[more]

PMID: 35700315

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