Ion Pairing and Multiple Ion Binding in Calcium Carbonate Solutions Based on a Polarizable AMOEBA Force Field and Ab Initio Molecular Dynamics

The speciation of calcium carbonate in water is important to the geochemistry of the world's oceans and has ignited significant debate regarding the mechanism by which nucleation occurs. Here, it is vital to be able to quantify the thermodynamics of ion pairing versus higher order association p...

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Main Authors: Raiteri, Paolo, Schuitemaker, Alicia, Gale, Julian
Format: Journal Article
Language:English
Published: AMER CHEMICAL SOC 2020
Subjects:
Online Access:http://purl.org/au-research/grants/arc/FT130100463
http://hdl.handle.net/20.500.11937/84792
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author Raiteri, Paolo
Schuitemaker, Alicia
Gale, Julian
author_facet Raiteri, Paolo
Schuitemaker, Alicia
Gale, Julian
author_sort Raiteri, Paolo
building Curtin Institutional Repository
collection Online Access
description The speciation of calcium carbonate in water is important to the geochemistry of the world's oceans and has ignited significant debate regarding the mechanism by which nucleation occurs. Here, it is vital to be able to quantify the thermodynamics of ion pairing versus higher order association processes in order to distinguish between possible pathways. Given that it is experimentally challenging to quantify such species, here we determine the thermodynamics for ion pairing and multiple binding of calcium carbonate species using bias-enhanced molecular dynamics. In order to examine the uncertainties underlying these results, we derived a new polarizable force field for both calcium carbonate and bicarbonate in water based on the AMOEBA model to compare against our earlier rigid ion model, both of which are further benchmarked against ab initio molecular dynamics for the ion pair. Both force fields consistently indicate that the association of calcium carbonate ion pairs to form larger species is stable, though with an equilibrium constant that is lower than for ion pairing itself.
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spelling curtin-20.500.11937-847922021-08-12T01:07:44Z Ion Pairing and Multiple Ion Binding in Calcium Carbonate Solutions Based on a Polarizable AMOEBA Force Field and Ab Initio Molecular Dynamics Raiteri, Paolo Schuitemaker, Alicia Gale, Julian Science & Technology Physical Sciences Chemistry, Physical Chemistry DIFFUSION-COEFFICIENTS DISSOCIATION-CONSTANTS SELF-DIFFUSION WATER MODEL SIMULATIONS DENSITY THERMODYNAMICS MECHANICS HYDRATION The speciation of calcium carbonate in water is important to the geochemistry of the world's oceans and has ignited significant debate regarding the mechanism by which nucleation occurs. Here, it is vital to be able to quantify the thermodynamics of ion pairing versus higher order association processes in order to distinguish between possible pathways. Given that it is experimentally challenging to quantify such species, here we determine the thermodynamics for ion pairing and multiple binding of calcium carbonate species using bias-enhanced molecular dynamics. In order to examine the uncertainties underlying these results, we derived a new polarizable force field for both calcium carbonate and bicarbonate in water based on the AMOEBA model to compare against our earlier rigid ion model, both of which are further benchmarked against ab initio molecular dynamics for the ion pair. Both force fields consistently indicate that the association of calcium carbonate ion pairs to form larger species is stable, though with an equilibrium constant that is lower than for ion pairing itself. 2020 Journal Article http://hdl.handle.net/20.500.11937/84792 10.1021/acs.jpcb.0c01582 English http://purl.org/au-research/grants/arc/FT130100463 http://purl.org/au-research/grants/arc/FL180100087 AMER CHEMICAL SOC fulltext
spellingShingle Science & Technology
Physical Sciences
Chemistry, Physical
Chemistry
DIFFUSION-COEFFICIENTS
DISSOCIATION-CONSTANTS
SELF-DIFFUSION
WATER
MODEL
SIMULATIONS
DENSITY
THERMODYNAMICS
MECHANICS
HYDRATION
Raiteri, Paolo
Schuitemaker, Alicia
Gale, Julian
Ion Pairing and Multiple Ion Binding in Calcium Carbonate Solutions Based on a Polarizable AMOEBA Force Field and Ab Initio Molecular Dynamics
title Ion Pairing and Multiple Ion Binding in Calcium Carbonate Solutions Based on a Polarizable AMOEBA Force Field and Ab Initio Molecular Dynamics
title_full Ion Pairing and Multiple Ion Binding in Calcium Carbonate Solutions Based on a Polarizable AMOEBA Force Field and Ab Initio Molecular Dynamics
title_fullStr Ion Pairing and Multiple Ion Binding in Calcium Carbonate Solutions Based on a Polarizable AMOEBA Force Field and Ab Initio Molecular Dynamics
title_full_unstemmed Ion Pairing and Multiple Ion Binding in Calcium Carbonate Solutions Based on a Polarizable AMOEBA Force Field and Ab Initio Molecular Dynamics
title_short Ion Pairing and Multiple Ion Binding in Calcium Carbonate Solutions Based on a Polarizable AMOEBA Force Field and Ab Initio Molecular Dynamics
title_sort ion pairing and multiple ion binding in calcium carbonate solutions based on a polarizable amoeba force field and ab initio molecular dynamics
topic Science & Technology
Physical Sciences
Chemistry, Physical
Chemistry
DIFFUSION-COEFFICIENTS
DISSOCIATION-CONSTANTS
SELF-DIFFUSION
WATER
MODEL
SIMULATIONS
DENSITY
THERMODYNAMICS
MECHANICS
HYDRATION
url http://purl.org/au-research/grants/arc/FT130100463
http://purl.org/au-research/grants/arc/FT130100463
http://hdl.handle.net/20.500.11937/84792