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Title: Uncovering the Atomistic Mechanism for Calcite Step Growth

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry, Curtin Institute for Computation/The Institute for Geoscience Research (TIGeR), Curtin University, PO Box U1987 Perth WA 6845 Australia
  2. Chemical Sciences Division, Oak Ridge National Laboratory, PO Box 2008, MS-6110 Oak Ridge TN 37831 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1400833
Grant/Contract Number:
ERKCC72
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 29; Related Information: CHORUS Timestamp: 2017-12-04 09:39:04; Journal ID: ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

De La Pierre, Marco, Raiteri, Paolo, Stack, Andrew G., and Gale, Julian D.. Uncovering the Atomistic Mechanism for Calcite Step Growth. Germany: N. p., 2017. Web. doi:10.1002/anie.201701701.
De La Pierre, Marco, Raiteri, Paolo, Stack, Andrew G., & Gale, Julian D.. Uncovering the Atomistic Mechanism for Calcite Step Growth. Germany. doi:10.1002/anie.201701701.
De La Pierre, Marco, Raiteri, Paolo, Stack, Andrew G., and Gale, Julian D.. Thu . "Uncovering the Atomistic Mechanism for Calcite Step Growth". Germany. doi:10.1002/anie.201701701.
@article{osti_1400833,
title = {Uncovering the Atomistic Mechanism for Calcite Step Growth},
author = {De La Pierre, Marco and Raiteri, Paolo and Stack, Andrew G. and Gale, Julian D.},
abstractNote = {},
doi = {10.1002/anie.201701701},
journal = {Angewandte Chemie (International Edition)},
number = 29,
volume = 56,
place = {Germany},
year = {Thu Apr 13 00:00:00 EDT 2017},
month = {Thu Apr 13 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/anie.201701701

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  • 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 (CaCO 3) in water, computer simulations have been used in this paper 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 Ca 2+ only adsorbs after CO 3 2-. In contrast to the conventional picture, ion pairs prefer to bind at themore » upper edge of the step with only one ion, at most, coordinated to the step and lower terrace. Finally, 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.« less
  • Cited by 3
  • We present elucidation of homoepitaxial growth mechanisms on vicinal non-polar surfaces of GaN that is highly important for gaining an understanding of and control thin film surface morphology and properties. Using first-principles calculations, we study the step-flow growth in m-plane GaN based on atomic row nucleation and kink propagation kinetics. Ga–N dimer adsorption onto the m-plane is energetically more favorable than that of Ga and N isolated adatoms. Therefore, we have treated the dimers as the dominant growth species attached to the step edges. By calculating the free energies of sequentially attached Ga–N dimers, we have elucidated that the a-stepmore » edge kink growth proceeds by parallel attachment rather than by across the step edge approach. We found a series of favorable configurations of kink propagation and calculated the free energy and nucleation barriers for kink evolution on five types of step edges (a, +c, -c, +a + c, and -a - c). By changing the chemical potential μGa and the excess chemical potential Δμ, the growth velocities at the five types of edges are controlled by the corresponding kink pair nucleation barrier E* in their free energy profiles. To explore the kink-flow growth instability observed at different Ga/N flux ratios, calculations of kink pairs on the incompact -c and +c-step edges are further performed to study their formation energies. Variations of these step edge morphologies with a tuned chemical environment are consistent with previous experimental observations, including stable diagonal ±a ± c-direction steps. In conclusion, our work provides a first-principles approach to explore step growth and surface morphology of the vicinal m-plane GaN, which is applicable to analyze and control the step-flow growth of other binary thin films.« less
  • The authors present novel in situ observations of the dynamics of monomolecular growth steps on calcite. Steps do not interact at separations of [approximately]10 nm and above, indicating that surface diffusion does not control calcite growth. Instead, steps advance by material addition from solution onto step sites or a narrow adjacent zone. Step nucleation is primarily at growth spirals, and no spontaneous surface nucleation is observed; growth rate is controlled by spiral rotation rate. Thus, classical growth models based on rapid surface diffusion are inapplicable to calcite and possible to many other minerals. 23 refs., 4 figs., 2 tabs.