Uncovering the Atomistic Mechanism for Calcite Step Growth

Marco De La Pierre; Paolo Raiteri; Andrew G. Stack; Julian D. Gale

doi:10.1002/anie.201701701

Uncovering the Atomistic Mechanism for Calcite Step Growth

Marco De La Pierre, Paolo Raiteri, Andrew G. Stack, Julian D. Gale

Geochemistry & Interfacial Science

Research output: Contribution to journal › Article › peer-review

49 Scopus citations

Abstract

Determining a complete atomic-level picture of how minerals grow from aqueous solution remains a challenge as macroscopic rates can be a convolution of many reactions. For the case of calcite (CaCO₃) in water, computer simulations have been used to map the complex thermodynamic landscape leading to growth of the two distinct steps, acute and obtuse, on the basal surface. The carbonate ion is found to preferentially adsorb at the upper edge of acute steps while Ca²⁺ only adsorbs after CO₃²⁻. In contrast to the conventional picture, ion pairs prefer to bind at the upper edge of the step with only one ion, at most, coordinated to the step and lower terrace. Migration of the first carbonate ion to a growth site is found to be rate-limiting for kink nucleation, with this process having a lower activation energy on the obtuse step.

Original language	English
Pages (from-to)	8464-8467
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	29
DOIs	https://doi.org/10.1002/anie.201701701
State	Published - Jul 10 2017

Funding

P.R. and J.D.G. acknowledge funding from the Australian Research Council and the use of resources provided by the Pawsey Supercomputing Centre with funding from the Governments of Australia and Western Australia. A.G.S. was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division.

Funders	Funder number
Governments of Australia and Western Australia
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Chemical Sciences, Geosciences, and Biosciences Division
Australian Research Council	FT130100463, DP160100677

Keywords

calcite
crystal growth
free energy
molecular dynamics

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10.1002/anie.201701701

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abstract = "Determining a complete atomic-level picture of how minerals grow from aqueous solution remains a challenge as macroscopic rates can be a convolution of many reactions. For the case of calcite (CaCO3) in water, computer simulations have been used to map the complex thermodynamic landscape leading to growth of the two distinct steps, acute and obtuse, on the basal surface. The carbonate ion is found to preferentially adsorb at the upper edge of acute steps while Ca2+ only adsorbs after CO32−. In contrast to the conventional picture, ion pairs prefer to bind at the upper edge of the step with only one ion, at most, coordinated to the step and lower terrace. Migration of the first carbonate ion to a growth site is found to be rate-limiting for kink nucleation, with this process having a lower activation energy on the obtuse step.",

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Uncovering the Atomistic Mechanism for Calcite Step Growth

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