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    Determining the Adsorption Free Energies of Small Organic Molecules and Intrinsic Ions at the Terrace and Steps of Calcite

    91327.pdf (5.581Mb)
    Access Status
    Open access
    Authors
    Aufort, Julie
    Schuitemaker, Alicia
    Green, R.
    Demichelis, Raffaella
    Raiteri, Paolo
    Gale, Julian
    Date
    2022
    Type
    Journal Article
    
    Metadata
    Show full item record
    Citation
    Aufort, J. and Schuitemaker, A. and Green, R. and Demichelis, R. and Raiteri, P. and Gale, J.D. 2022. Determining the Adsorption Free Energies of Small Organic Molecules and Intrinsic Ions at the Terrace and Steps of Calcite. Crystal Growth and Design. 22 (2): pp. 1445-1458.
    Source Title
    Crystal Growth and Design
    DOI
    10.1021/acs.cgd.1c01414
    ISSN
    1528-7483
    Faculty
    Faculty of Science and Engineering
    School
    School of Molecular and Life Sciences (MLS)
    Funding and Sponsorship
    http://purl.org/au-research/grants/arc/DP16100677
    http://purl.org/au-research/grants/arc/FT18100385
    http://purl.org/au-research/grants/arc/FL180100087
    Remarks

    This document is the Accepted Manuscript version of a Published Work that appeared in final form in Crystal Growth and Design, copyright © American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/acs.cgd.1c01414

    URI
    http://hdl.handle.net/20.500.11937/91503
    Collection
    • Curtin Research Publications
    Abstract

    The adsorption of small molecules containing two different organic functional groups at terrace and step sites on the {101¯ 4} surface of calcite at the interface with aqueous solution was studied using free energy methods. For comparison, the adsorption free energies of the component ions of calcium carbonate were also determined at the same sites. Polarizability was taken into account through using a force field developed for calcium carbonate based on the AMOEBA model that contains static multipoles and self-consistent induced dipoles. The influence of including polarization was examined by comparing to data obtained with a fixed charge rigid-ion model. The strong hydration layers above the basal plane of calcite were shown to hinder the direct attachment of the small species studied, including the constituent ions of the mineral. Only the species bearing an amino group, namely, methylammonium and glycine, demonstrated favorable adsorption free energies. The ability of amino groups to more readily pass through the hydration layers than carboxylate and carbonate groups can be explained by their weaker solvation free energies, while the carbonate ions within the calcite surface with which they bind are also less strongly hydrated than calcium ions. Acetate, glycine, and methylammonium were all found to be able to directly bind to one growth site at the acute step of calcite. This is at variance with results obtained with a rigid-ion model in which all binding free energies are endergonic. Thus, including polarization allows for a description of the adsorption process that is more consistent with experimental observations, particularly at calcite steps, and for determination of more reliable atomic-scale mechanisms for calcite growth and its modification by organic additives. Even with polarization, the organic functional groups considered only exhibit moderate binding to calcite steps with adsorption free energies not exceeding -13 kJ/mol.

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