Investigating the effect of Cu$^{2+}$ sorption in montmorillonite using density functional theory and molecular dynamics simulations

Fuente: arXiv
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Auteurs principaux: Pedram, Yalda, Zhang, Yaoting, Briggs, Scott, Kim, Chang Seok, Brochard, Laurent, Kalinichev, Andrey G., Béland, Laurent Karim
Format: Preprint
Publié: 2023
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author Pedram, Yalda
Zhang, Yaoting
Briggs, Scott
Kim, Chang Seok
Brochard, Laurent
Kalinichev, Andrey G.
Béland, Laurent Karim
author_facet Pedram, Yalda
Zhang, Yaoting
Briggs, Scott
Kim, Chang Seok
Brochard, Laurent
Kalinichev, Andrey G.
Béland, Laurent Karim
contents Montmorillonite (MMT) is the main mineral component of bentonite, which is currently proposed as a sealing material in deep geological repositories (DGRs) for used nuclear fuel. In the Canadian program, which will utilize copper-cladded used fuel containers, safety analysis considers the effect of copper corrosion, during which Cu$^{2+}$ ions could potentially be adsorbed by the surrounding MMT. In such a scenario, ion exchange between Na$^+$ and Cu$^{2+}$ is expected. In this study, a multiscale approach that combines electronic density functional theory (DFT) and force-field-based molecular dynamics (MD) simulations was employed to study the effect of introducing Cu$^{2+}$ ions to MMT. An extension to the ClayFF force field is parametrized and validated using DFT to model how Cu$^{2+}$ interacts with clay systems. MD simulations were performed to calculate the interaction free energies between MMT platelets containing Cu$^{2+}$ ions (Cu-MMT) and compared them to inter-platelet interaction energies in Na-MMT and Ca-MMT. Our calculations suggest Cu-MMT develops swelling pressures between those of Ca-MMT and Na-MMT. Furthermore, our MD simulations suggest that Cu$^{2+}$ has MMT interlayer mobility that is significantly slower than that of Ca$^{2+}$.
format Preprint
id arxiv_https___arxiv_org_abs_2311_11139
institution arXiv
publishDate 2023
record_format arxiv
spellingShingle Investigating the effect of Cu$^{2+}$ sorption in montmorillonite using density functional theory and molecular dynamics simulations
Pedram, Yalda
Zhang, Yaoting
Briggs, Scott
Kim, Chang Seok
Brochard, Laurent
Kalinichev, Andrey G.
Béland, Laurent Karim
Materials Science
Computational Physics
Montmorillonite (MMT) is the main mineral component of bentonite, which is currently proposed as a sealing material in deep geological repositories (DGRs) for used nuclear fuel. In the Canadian program, which will utilize copper-cladded used fuel containers, safety analysis considers the effect of copper corrosion, during which Cu$^{2+}$ ions could potentially be adsorbed by the surrounding MMT. In such a scenario, ion exchange between Na$^+$ and Cu$^{2+}$ is expected. In this study, a multiscale approach that combines electronic density functional theory (DFT) and force-field-based molecular dynamics (MD) simulations was employed to study the effect of introducing Cu$^{2+}$ ions to MMT. An extension to the ClayFF force field is parametrized and validated using DFT to model how Cu$^{2+}$ interacts with clay systems. MD simulations were performed to calculate the interaction free energies between MMT platelets containing Cu$^{2+}$ ions (Cu-MMT) and compared them to inter-platelet interaction energies in Na-MMT and Ca-MMT. Our calculations suggest Cu-MMT develops swelling pressures between those of Ca-MMT and Na-MMT. Furthermore, our MD simulations suggest that Cu$^{2+}$ has MMT interlayer mobility that is significantly slower than that of Ca$^{2+}$.
title Investigating the effect of Cu$^{2+}$ sorption in montmorillonite using density functional theory and molecular dynamics simulations
topic Materials Science
Computational Physics
url https://arxiv.org/abs/2311.11139