DFT-CES2: Quantum Mechanics Based Embedding for Mean-Field QM/MM of Solid–Liquid Interfaces
Creators
- 1. Department of Chemistry
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2.
Korea Advanced Institute of Science and Technology
- 3. School of Energy and Chemical Engineering
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4.
Ulsan National Institute of Science and Technology
- 5. Division of Chemical Engineering and Bioengineering
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6.
Kangwon National University
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7.
California Institute of Technology
Abstract
The solid–liquid interface plays a crucial role in governing complex chemical phenomena, such as heterogeneous catalysis and (photo)electrochemical processes. Despite its importance, acquiring atom-scale information about these buried interfaces remains highly challenging, which has led to an increasing demand for reliable atomic simulations of solid–liquid interfaces. Here, we introduce an innovative first-principles-based multiscale simulation approach called DFT-CES2, a mean-field QM/MM method. To accurately model interactions at the interface, we developed a quantum-mechanics-based embedding scheme that partitions complex noncovalent interactions into Pauli repulsion, Coulomb (including polarization), and London dispersion energies, which are described using atom-dependent transferable parameters. As validated by comparison with high-level quantum mechanical energies, DFT-CES2 demonstrates chemical accuracy in describing interfacial interactions. DFT-CES2 enables the investigation of complex solid–liquid interfaces while avoiding extensive parametrization. Therefore, we expect DFT-CES2 to be broadly applicable for elucidating atom-scale details of large scale solid–liquid interfaces for multicomponent systems.
Copyright and License
Copyright © 2025 The Authors. Published by American Chemical Society
This publication is licensed under CC-BY-NC-ND 4.0 .
Data Availability
Supplemental Material
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacsau.5c00176.
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Notes on the derivations of mean atomic forces for DFT optimization and external forces on MM particles, error estimations, atom-dependent repulsion parametrization details, computational details, and coupling of alchemical free energy method to DFT-CES2; figures illustrating linear correlation relating Rab0 to atomic polarizability, distribution of a point charge to grid points, syntax examples of new commands for DFT-CES2, header structure of the wrapper script, atomic polarizabilities of individual atoms in transition metal oxides, optimizations of atom-dependent repulsion parameters for N, S, alkali metal ions, halide ions, and rare gas atoms, optimization of scaling parameters for dispersion energy, comparison of DFT-CES2 energy with CCSD(T) binding energy for alkali metal ions, halide ions, and rare gas atoms, benchmarks of hydrogen bonded dimer interactions, DFT cells for oxide systems, and thermodynamic integration results for various oxide-water systems; tables of comparisons between nonorthgonalized and approximately orthgonalized wave functions, benchmarks of DFT-CES2 molecular interaction energies (using A24, S22, water interaction sets), performance comparisons of DFT-CES2 energies with other QM/MM methods, and benchmarks of molecule adsorption energies on metals and graphene; compressed example file for DFT-CES2 simulations (PDF)
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Examples of input files and wrapper script (ZIP)
Funding
This work was supported by the National Research Foundation of Korea (NRF), grants funded by the Korean government (MSIT) (Nos. 2021R1A2C2009643, RS-2024-00405261 and RS-2024-00450102).
Conflict of Interest
The authors declare no competing financial interest.
Acknowledgement
The authors express gratitude for supercomputing resources provided by the Korea Institute of Science and Technology Information (KSC-2021-CRE-0277).
Additional details
Funding
- National Research Foundation of Korea
- RS-2024-00405261
- National Research Foundation of Korea
- RS-2024-00450102
- National Research Foundation of Korea
- 2021R1A2C2009643
- Korea Institute of Science and Technology
- KSC-2021-CRE-0277
Dates
- Available
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2025-04-12