Determining the Complete Stability of Calcite Kink Sites: Real vs Ideal

Kink sites play a pivotal role in the growth and dissolution of materials at the solid-liquid interface. Despite this, little is known about the thermodynamic stability of such sites. Calcium carbonate, in the form of calcite, is one of the most abundant biominerals and a natural means of carbon seq...

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Main Authors: Armstrong, Blake I., Silvestri, Alessandro, De La Pierre, Marco, Raiteri, Paolo, Gale, Julian D.
Format: Journal Article
Published: 2023
Online Access:http://purl.org/au-research/grants/arc/FL180100087
http://hdl.handle.net/20.500.11937/96481
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author Armstrong, Blake I.
Silvestri, Alessandro
De La Pierre, Marco
Raiteri, Paolo
Gale, Julian D.
author_facet Armstrong, Blake I.
Silvestri, Alessandro
De La Pierre, Marco
Raiteri, Paolo
Gale, Julian D.
author_sort Armstrong, Blake I.
building Curtin Institutional Repository
collection Online Access
description Kink sites play a pivotal role in the growth and dissolution of materials at the solid-liquid interface. Despite this, little is known about the thermodynamic stability of such sites. Calcium carbonate, in the form of calcite, is one of the most abundant biominerals and a natural means of carbon sequestration in the environment. Here, we present a complete determination of the standard free energies for all 16 individual kink sites for the significant case of the calcite (101̅4)-water interface using both alchemical- and pathway-based simulation techniques. The results reveal the importance of distinguishing between real and ideal ion-binding free energies at surfaces, especially for calcite-water, where the interfacial potential can alter values by more than 100 kJ/mol per site. Individual kink site stabilities are found to show variations in excess of 60 kJ/mol, which can help explain the observed differences in growth rates between the two distinct steps of calcite.
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spelling curtin-20.500.11937-964812025-01-14T01:49:12Z Determining the Complete Stability of Calcite Kink Sites: Real vs Ideal Armstrong, Blake I. Silvestri, Alessandro De La Pierre, Marco Raiteri, Paolo Gale, Julian D. Kink sites play a pivotal role in the growth and dissolution of materials at the solid-liquid interface. Despite this, little is known about the thermodynamic stability of such sites. Calcium carbonate, in the form of calcite, is one of the most abundant biominerals and a natural means of carbon sequestration in the environment. Here, we present a complete determination of the standard free energies for all 16 individual kink sites for the significant case of the calcite (101̅4)-water interface using both alchemical- and pathway-based simulation techniques. The results reveal the importance of distinguishing between real and ideal ion-binding free energies at surfaces, especially for calcite-water, where the interfacial potential can alter values by more than 100 kJ/mol per site. Individual kink site stabilities are found to show variations in excess of 60 kJ/mol, which can help explain the observed differences in growth rates between the two distinct steps of calcite. 2023 Journal Article http://hdl.handle.net/20.500.11937/96481 10.1021/acs.jpcc.3c02864 http://purl.org/au-research/grants/arc/FL180100087 fulltext
spellingShingle Armstrong, Blake I.
Silvestri, Alessandro
De La Pierre, Marco
Raiteri, Paolo
Gale, Julian D.
Determining the Complete Stability of Calcite Kink Sites: Real vs Ideal
title Determining the Complete Stability of Calcite Kink Sites: Real vs Ideal
title_full Determining the Complete Stability of Calcite Kink Sites: Real vs Ideal
title_fullStr Determining the Complete Stability of Calcite Kink Sites: Real vs Ideal
title_full_unstemmed Determining the Complete Stability of Calcite Kink Sites: Real vs Ideal
title_short Determining the Complete Stability of Calcite Kink Sites: Real vs Ideal
title_sort determining the complete stability of calcite kink sites: real vs ideal
url http://purl.org/au-research/grants/arc/FL180100087
http://hdl.handle.net/20.500.11937/96481