Accurate quantum-chemical fragmentation calculations for ion–water clusters with the density-based many-body expansion

Schürmann, Stefanie; Vornweg, Johannes R.; Wolter, Mario; Jacob, Christoph R.

doi:10.1039/d2cp04539g

Cited by 11 publications

(28 citation statements)

References 83 publications

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“…To improve upon the eb-MBE, we recently proposed a density-based many-body expansion (db-MBE), 44,45 which is motivated by the observation that the MBE of the electron density [eq 2] seems to converge faster than the MBE of the total energy [eq 1]. 42 The db-MBE represents a generalization of subsystem DFT 43 and can be formulated as an ONIOMstyle multilevel approach, 47,48…”

Section: ■ Computational Methodologymentioning

confidence: 99%

“…only. Therefore, while in our previous work, we applied the db-MBE only in combination with DFT calculations, ,, it can be extended to any quantum-chemical method that provides an electron density, including wave function-based methods such as coupled cluster theory.…”

Section: Computational Methodologymentioning

confidence: 99%

“…The molecular structures of all considered structures have been taken from refs − and are also available in the Supporting Information of refs , .…”

Section: Computational Methodologymentioning

confidence: 99%

“…challenging for the MBEs, since larger higher-order contributions can be expected due to the polarizability of the water molecules. Previously, 45 we investigated the accuracy of the relative energies of these isomers of (H Here, we apply CCSD(T) for the eb-MBE and combine it with a density-based correction evaluated with HF densities for the db-MBE. The errors of the two-body and three-body eb-MBE and db-MBE for the protonated and deprotonated water hexamers are shown in Figure 3c,d.…”

Section: The Journal Of Physical Chemistrymentioning

confidence: 99%

“…Previously, we applied this db-MBE in combination with DFT calculations for the fragments and assessed its accuracy for water clusters as well as ion–water clusters . We showed that a two-body db-MBE already achieves an excellent accuracy for these test cases, which generally rivals the accuracy of a three-body eb-MBE.…”

Section: Introductionmentioning

confidence: 96%

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Coupled-Cluster Density-Based Many-Body Expansion

Focke,

Jacob

2023

J. Phys. Chem. A

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While CCSD(T) is often considered the “gold standard” of computational chemistry, the scaling of its computational cost as N7 limits its applicability for large and complex molecular systems. In this work, we apply the density-based many-body expansion [e26228Int. J. Quantum Chem.2020120] in combination with CCSD(T). The accuracy of this approach is assessed for neutral, protonated, and deprotonated water hexamers, as well as (H2O)16 and (H2O)17 clusters. For the neutral water clusters, we find that already with a density-based two-body expansion, we are able to approximate the supermolecular CCSD(T) energies within chemical accuracy (4 kJ/mol). This surpasses the accuracy that is achieved with a conventional, energy-based three-body expansion. We show that this accuracy can be maintained even when approximating the electron densities using Hartree–Fock instead of using coupled-cluster densities. The density-based many-body expansion thus offers a simple, resource-efficient, and highly parallelizable approach that makes CCSD(T)-quality calculations feasible where they would otherwise be prohibitively expensive.

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Section: ■ Computational Methodologymentioning

confidence: 99%

Section: Computational Methodologymentioning

confidence: 99%

“…The molecular structures of all considered structures have been taken from refs − and are also available in the Supporting Information of refs , .…”

Section: Computational Methodologymentioning

confidence: 99%

Section: The Journal Of Physical Chemistrymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 96%

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Coupled-Cluster Density-Based Many-Body Expansion

Focke,

Jacob

2023

J. Phys. Chem. A

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Subsystem density‐functional theory (update)

Jacob,

Neugebauer

2024

WIREs Comput Mol Sci

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The past years since the publication of our review on subsystem density‐functional theory (sDFT) (WIREs Comput Mol Sci. 2014, 4:325–362) have witnessed a rapid development and diversification of quantum mechanical fragmentation and embedding approaches related to sDFT and frozen‐density embedding (FDE). In this follow‐up article, we provide an update addressing formal and algorithmic work on sDFT/FDE, novel approximations developed for treating the non‐additive kinetic energy in these DFT/DFT hybrid methods, new areas of application and extensions to properties previously not accessible, projection‐based techniques as an alternative to solely density‐based embedding, progress in wavefunction‐in‐DFT embedding, new fragmentation strategies in the context of DFT which are technically or conceptually similar to sDFT, and the blurring boundary between advanced DFT/MM and approximate DFT/DFT embedding methods.This article is categorized under: Electronic Structure Theory > Density Functional Theory

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Protein–Ligand Interaction Energies from Quantum-Chemical Fragmentation Methods: Upgrading the MFCC-Scheme with Many-Body Contributions

Vornweg,

Jacob

2024

J. Phys. Chem. B

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Quantum-chemical fragmentation methods offer an attractive approach for the accurate calculation of protein−ligand interaction energies. While the molecular fractionation with conjugate caps (MFCC) scheme offers a rather straightforward approach for this purpose, its accuracy is often not sufficient. Here, we upgrade the MFCC scheme for the calculation of protein−ligand interactions by including many-body contributions. The resulting fragmentation scheme is an extension of our previously developed MFCC-MBE(2) scheme [J. Comput. Chem. 2023, 44, 1634−1644. For a diverse test set of protein−ligand complexes, we demonstrate that by upgrading the MFCC scheme with many-body contributions, the error in protein−ligand interaction energies can be reduced significantly, and one generally achieves errors below 20 kJ/mol. Our scheme allows for systematically reducing these errors by including higher-order many-body contributions. As it combines the use of single amino acid fragments with high accuracy, our scheme provides an ideal starting point for the parametrization of accurate machine learning potentials for proteins and protein−ligand interactions.

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Accurate quantum-chemical fragmentation calculations for ion–water clusters with the density-based many-body expansion

Abstract: The many-body expansion (MBE) provides an attractive fragmentation method for the efficient quantum-chemical treatment of molecular clusters. However, its convergence with the many-body order is generally slow for molecular clusters...

Cited by 11 publications

References 83 publications

Coupled-Cluster Density-Based Many-Body Expansion

Coupled-Cluster Density-Based Many-Body Expansion

Subsystem density‐functional theory (update)

Protein–Ligand Interaction Energies from Quantum-Chemical Fragmentation Methods: Upgrading the MFCC-Scheme with Many-Body Contributions

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