Embedding Beyond Electrostatics: The Extended Polarizable Density Embedding Model

Willem Van den Heuvel, Peter Reinholdt, Jacob Kongsted*


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The polarizable density embedding (PDE) model is a focused QM/QM fragment-based embedding model designed to model solvation effects on molecular properties. We extend the PDE model to include exchange and nonadditive exchange-correlation (for DFT) in the embedding potential in addition to the existing electrostatic, polarization, and nonelectrostatic effects already present. The resulting model, termed PDE-X, yields localized electronic excitation energies that accurately capture the range dependence of the solvent interaction and gives close agreement with full quantum mechanical (QM) results, even when using minimal QM regions. We show that the PDE-X embedding description consistently improves the accuracy of excitation energies for a diverse set of organic chromophores. The improved embedding description leads to systematic solvent effects that do not average out when applying configurational sampling.

TidsskriftJournal of Physical Chemistry B
Udgave nummer14
Sider (fra-til)3248-3256
StatusUdgivet - apr. 2023

Bibliografisk note

Funding Information:
Computations/simulations for the work described herein were supported by the DeIC National HPC Centre, SDU. We acknowledge the Independent Research Fund Denmark for financial support (Grant ID: DFF-7014-00050B) and the Novo Nordisk Foundation (Grant ID: NNF19OC0058144) for financial support.

Publisher Copyright:
© 2023 American Chemical Society


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