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Reconciling work functions and adsorption enthalpies for implicit solvent: a Pt (111)/water interface case study

Reconciling work functions and adsorption enthalpies for implicit solvent: a Pt (111)/water interface case study
Reconciling work functions and adsorption enthalpies for implicit solvent: a Pt (111)/water interface case study
Implicit solvent models are a computationally efficient method of representing solid/liquid interfaces prevalent in electrocatalysis, energy storage and materials science. However, electronic structure changes induced at the metallic surface by the dielectric continuum are not fully understood. To address this, we perform DFT calculations for the Pt(111)/water interface, in order to compare Poisson-Boltzmann continuum solvation methods with ab initio molecular dynamics (AIMD) simulations of explicit solvent. We show that the implicit solvent cavity can be parametrized in terms of the electric dipole moment change at the equilibrated explicit Pt/water interface to obtain the potential of zero charge (PZC). We also compare the accuracy of aqueous enthalpies of adsorption of phenol on Pt(111) using geometry and charge density based dielectric cavitation methods. The ability to parametrize the cavity according to individual atoms, as afforded in the geometry based approach, is key to obtaining accurate enthalpy changes of adsorption under aqueous conditions. We also show that the electronic structure changes induced by explicit solvent and our proposed implicit solvent parametrization scheme yield comparable density difference profiles and d-band projected density of states. We therefore demonstrate the capability of implicit solvent approaches to capture both the energetics of adsorption processes and the main electronic effects of aqueous solvent on the metallic surface. This work therefore provides a scheme for computationally efficient simulations of interfacial processes for applications in areas such as heterogeneous catalysis and electrochemistry.
ab initio molecular dynamics, continuum solvation, metal/water interfaces, phenol adsorption
1549-9618
2703-2715
Bramley, Gabriel, Adrian
3ed28a08-44fe-4c51-bd9e-7a9309247c1b
Nguyen, Manh-Thuong
6ad86d09-8f27-4d61-90b6-4f76b912f299
Glezakou, Vassiliki-Alexandra
1252b310-9674-4b5d-95fb-5e45a44f3068
Rousseau, Roger
3588ba57-c98b-43bc-86cd-7be0191ba798
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Bramley, Gabriel, Adrian
3ed28a08-44fe-4c51-bd9e-7a9309247c1b
Nguyen, Manh-Thuong
6ad86d09-8f27-4d61-90b6-4f76b912f299
Glezakou, Vassiliki-Alexandra
1252b310-9674-4b5d-95fb-5e45a44f3068
Rousseau, Roger
3588ba57-c98b-43bc-86cd-7be0191ba798
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61

Bramley, Gabriel, Adrian, Nguyen, Manh-Thuong, Glezakou, Vassiliki-Alexandra, Rousseau, Roger and Skylaris, Chris-Kriton (2020) Reconciling work functions and adsorption enthalpies for implicit solvent: a Pt (111)/water interface case study. Journal of Chemical Theory and Computation, 16 (4), 2703-2715. (doi:10.1021/acs.jctc.0c00034).

Record type: Article

Abstract

Implicit solvent models are a computationally efficient method of representing solid/liquid interfaces prevalent in electrocatalysis, energy storage and materials science. However, electronic structure changes induced at the metallic surface by the dielectric continuum are not fully understood. To address this, we perform DFT calculations for the Pt(111)/water interface, in order to compare Poisson-Boltzmann continuum solvation methods with ab initio molecular dynamics (AIMD) simulations of explicit solvent. We show that the implicit solvent cavity can be parametrized in terms of the electric dipole moment change at the equilibrated explicit Pt/water interface to obtain the potential of zero charge (PZC). We also compare the accuracy of aqueous enthalpies of adsorption of phenol on Pt(111) using geometry and charge density based dielectric cavitation methods. The ability to parametrize the cavity according to individual atoms, as afforded in the geometry based approach, is key to obtaining accurate enthalpy changes of adsorption under aqueous conditions. We also show that the electronic structure changes induced by explicit solvent and our proposed implicit solvent parametrization scheme yield comparable density difference profiles and d-band projected density of states. We therefore demonstrate the capability of implicit solvent approaches to capture both the energetics of adsorption processes and the main electronic effects of aqueous solvent on the metallic surface. This work therefore provides a scheme for computationally efficient simulations of interfacial processes for applications in areas such as heterogeneous catalysis and electrochemistry.

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Accepted/In Press date: 17 March 2020
e-pub ahead of print date: 17 March 2020
Published date: 14 April 2020
Additional Information: Funding Information: G.B. (partial support), V.-A.G., M.-T.N., and R.R. were supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemistry, Geochemistry and Biological Sciences, and located at Pacific Northwest National Laboratory (PNNL). Computational resources were provided by National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility located at Lawrence Berkeley National Laboratory (LBNL). PNNL is operated by Battelle for the US Department of Energy under Contract DE-AC05-76RL01830. Computational resources were provided by PNNL Research Computing and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science of the U.S. DOE, located at Lawrence Berkeley national lab (LBNL). G.B. acknowledges the EPSRC for partial support in PhD funding. The authors acknowledge the use of the IRIDIS High Performance Computing Facility (IRIDIS 5) and associated support services at the University of Southampton in the completion of this work. We are grateful to the UK Materials and Molecular Modelling Hub (Thomas HPC) for computational resources, which is partially funded by EPSRC (EP/P020194/1). Publisher Copyright: Copyright © 2020 American Chemical Society.
Keywords: ab initio molecular dynamics, continuum solvation, metal/water interfaces, phenol adsorption

Identifiers

Local EPrints ID: 439008
URI: http://eprints.soton.ac.uk/id/eprint/439008
ISSN: 1549-9618
PURE UUID: 9daaa878-f0cc-4eda-b2b6-f5d21302f9b3
ORCID for Chris-Kriton Skylaris: ORCID iD orcid.org/0000-0003-0258-3433

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Date deposited: 31 Mar 2020 16:31
Last modified: 21 Sep 2022 04:01

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Contributors

Author: Gabriel, Adrian Bramley
Author: Manh-Thuong Nguyen
Author: Vassiliki-Alexandra Glezakou
Author: Roger Rousseau

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