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Practical approach to large-scale electronic structure calculations in electrolyte solutions via continuum-embedded linear-scaling density functional theory

Practical approach to large-scale electronic structure calculations in electrolyte solutions via continuum-embedded linear-scaling density functional theory
Practical approach to large-scale electronic structure calculations in electrolyte solutions via continuum-embedded linear-scaling density functional theory

We present the implementation of a hybrid continuum-atomistic model for including the effects of a surrounding electrolyte in large-scale density functional theory (DFT) calculations within the Order-N Electronic Total Energy Package (ONETEP) linear-scaling DFT code, which allows the simulation of large complex systems such as electrochemical interfaces. The model represents the electrolyte ions as a scalar field and the solvent as a polarizable dielectric continuum, both surrounding the quantum solute. The overall energy expression is a grand canonical functional incorporating the electron kinetic and exchange-correlation energies, the total electrostatic energy, entropy, and chemical potentials of the surrounding electrolyte, osmotic pressure, and the effects of cavitation, dispersion, and repulsion. The DFT calculation is performed fully self-consistently in the electrolyte model, allowing the quantum-mechanical system and the surrounding continuum environment to interact and mutually polarize. A bespoke highly parallel multigrid Poisson-Boltzmann solver library, DL-MG, deals with the electrostatic problem, solving a generalized Poisson-Boltzmann equation. Our model supports open boundary conditions, which allows the treatment of molecules, entire biomolecules, or larger nanoparticle assemblies in the electrolyte. We have also implemented the model for periodic boundary conditions, allowing the treatment of extended systems such as electrode surfaces in contact with the electrolyte. A key feature of the model is the use of solute size and solvation-shell-aware accessibility functions that prevent the unphysical accumulation of electrolyte charge near the quantum solute boundary. The model has a small number of parameters - here we demonstrate their calibration against experimental mean activity coefficients. We also present an exemplar simulation of an 1634-atom model of the interface between a graphite anode and LiPF 6 electrolyte in an ethylene carbonate solvent. We compare the cases where Li atoms are intercalated at opposite edges of the graphite slab and in solution, demonstrating a potential application of the model in simulations of fundamental processes in Li-ion batteries.

1932-7447
7860-7872
Dziedzic, Jacek
8e2fdb55-dade-4ae4-bf1f-a148a89e4383
Bhandari, Arihant
f2f12a89-273f-4c5e-a52e-e21835aaacfc
Anton, Lucian
da3a4e52-cdd8-45c2-97c0-174cfb6cbc45
Peng, Chao
20f4467b-1786-4e11-97f2-2ab5885bcd7a
Womack, James C
ef9e1954-4a38-4e89-bf25-741a0738e85b
Famili, Marjan
24774b5a-ae1b-475f-951b-60cff5924d4f
Kramer, Denis
1faae37a-fab7-4edd-99ee-ae4c30d3cde4
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Dziedzic, Jacek
8e2fdb55-dade-4ae4-bf1f-a148a89e4383
Bhandari, Arihant
f2f12a89-273f-4c5e-a52e-e21835aaacfc
Anton, Lucian
da3a4e52-cdd8-45c2-97c0-174cfb6cbc45
Peng, Chao
20f4467b-1786-4e11-97f2-2ab5885bcd7a
Womack, James C
ef9e1954-4a38-4e89-bf25-741a0738e85b
Famili, Marjan
24774b5a-ae1b-475f-951b-60cff5924d4f
Kramer, Denis
1faae37a-fab7-4edd-99ee-ae4c30d3cde4
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61

Dziedzic, Jacek, Bhandari, Arihant, Anton, Lucian, Peng, Chao, Womack, James C, Famili, Marjan, Kramer, Denis and Skylaris, Chris-Kriton (2020) Practical approach to large-scale electronic structure calculations in electrolyte solutions via continuum-embedded linear-scaling density functional theory. The Journal of Physical Chemistry C, 124 (14), 7860-7872. (doi:10.1021/acs.jpcc.0c00762).

Record type: Article

Abstract

We present the implementation of a hybrid continuum-atomistic model for including the effects of a surrounding electrolyte in large-scale density functional theory (DFT) calculations within the Order-N Electronic Total Energy Package (ONETEP) linear-scaling DFT code, which allows the simulation of large complex systems such as electrochemical interfaces. The model represents the electrolyte ions as a scalar field and the solvent as a polarizable dielectric continuum, both surrounding the quantum solute. The overall energy expression is a grand canonical functional incorporating the electron kinetic and exchange-correlation energies, the total electrostatic energy, entropy, and chemical potentials of the surrounding electrolyte, osmotic pressure, and the effects of cavitation, dispersion, and repulsion. The DFT calculation is performed fully self-consistently in the electrolyte model, allowing the quantum-mechanical system and the surrounding continuum environment to interact and mutually polarize. A bespoke highly parallel multigrid Poisson-Boltzmann solver library, DL-MG, deals with the electrostatic problem, solving a generalized Poisson-Boltzmann equation. Our model supports open boundary conditions, which allows the treatment of molecules, entire biomolecules, or larger nanoparticle assemblies in the electrolyte. We have also implemented the model for periodic boundary conditions, allowing the treatment of extended systems such as electrode surfaces in contact with the electrolyte. A key feature of the model is the use of solute size and solvation-shell-aware accessibility functions that prevent the unphysical accumulation of electrolyte charge near the quantum solute boundary. The model has a small number of parameters - here we demonstrate their calibration against experimental mean activity coefficients. We also present an exemplar simulation of an 1634-atom model of the interface between a graphite anode and LiPF 6 electrolyte in an ethylene carbonate solvent. We compare the cases where Li atoms are intercalated at opposite edges of the graphite slab and in solution, demonstrating a potential application of the model in simulations of fundamental processes in Li-ion batteries.

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electrolyte_model_resub_jpc-c - Accepted Manuscript
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Accepted/In Press date: 11 March 2020
e-pub ahead of print date: 11 March 2020
Published date: 9 April 2020

Identifiers

Local EPrints ID: 439009
URI: http://eprints.soton.ac.uk/id/eprint/439009
ISSN: 1932-7447
PURE UUID: 5489603a-4518-418f-b515-b9c09f09afdb
ORCID for Jacek Dziedzic: ORCID iD orcid.org/0000-0003-4786-372X
ORCID for James C Womack: ORCID iD orcid.org/0000-0001-5497-4482
ORCID for Chris-Kriton Skylaris: ORCID iD orcid.org/0000-0003-0258-3433

Catalogue record

Date deposited: 31 Mar 2020 16:31
Last modified: 26 Nov 2021 05:17

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Contributors

Author: Jacek Dziedzic ORCID iD
Author: Arihant Bhandari
Author: Lucian Anton
Author: Chao Peng
Author: James C Womack ORCID iD
Author: Marjan Famili
Author: Denis Kramer

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