Analytic geometric gradients for the polarizable density embedding model

Peter Reinholdt, Willem Van den Heuvel, Jacob Kongsted*

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Abstract

The polarizable density embedding (PDE) model is an advanced fragment-based QM/QM embedding model closely related to the earlier polarizable embedding (PE) model. PDE features an improved description of permanent electrostatics and further includes non-electrostatic repulsion. We present an implementation of analytic geometric gradients for the PDE model, which allows for partial geometry optimizations of QM regions embedded in large molecular environments. We benchmark the quality of structures from PE-QM and PDE-QM geometry optimizations on a diverse set of small organic molecules embedded in four solvents. The PDE model performs well when targeting Hartree–Fock calculations, but density functional theory (DFT) calculations prove more challenging. We suggest a hybrid PDE-LJ model which produces solute–solvent structures of good quality for DFT. Finally, we apply the developed model to a theoretical estimation of the solvatochromic shift on the fluorescence emission energy of the environment-sensitive 4-aminophthalimide probe based on state-specific multiconfigurational PDE-QM calculations.

OriginalsprogEngelsk
Artikelnummere27177
TidsskriftInternational Journal of Quantum Chemistry
Vol/bind123
Udgave nummer18
Antal sider12
ISSN0020-7608
DOI
StatusUdgivet - 15. sep. 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 The Authors. International Journal of Quantum Chemistry published by Wiley Periodicals LLC.

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