Structure and Dynamics of Water at Step Edges on the Calcite {101̅4} Surface
The behavior of liquid water around obtuse and acute steps parallel to <4̅41> on the {101̅4} cleavage surface of calcite has been investigated by means of classical molecular dynamics simulations performed with a force-field fitted against thermodynamic properties. Water density maps, radial d...
| Main Authors: | , , |
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| Format: | Journal Article |
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American Chemical Society
2016
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| Online Access: | http://purl.org/au-research/grants/arc/FT130100463 http://hdl.handle.net/20.500.11937/23793 |
| _version_ | 1848751249541824512 |
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| author | De La Pierre, Marco Raiteri, Paolo Gale, Julian |
| author_facet | De La Pierre, Marco Raiteri, Paolo Gale, Julian |
| author_sort | De La Pierre, Marco |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | The behavior of liquid water around obtuse and acute steps parallel to <4̅41> on the {101̅4} cleavage surface of calcite has been investigated by means of classical molecular dynamics simulations performed with a force-field fitted against thermodynamic properties. Water density maps, radial distribution functions, and water average residence times have been investigated. The structure and dynamics of the first two ordered hydration layers, which have been previously observed for the basal surface of calcite, are found to be disrupted by the presence of the steps over a range of five molecular rows either side of the step edge. Calcium sites along the step top edge can coordinate up to three water molecules, as compared with just the single water that can be adsorbed per calcium ion on the flat surface. Water residence times at calcium sites in the vicinity of the step span greater than 2 orders of magnitude, from tenths to several tens of ns, as compared to 2 and 0.2 ns for the flat surface and a calcium ion in aqueous solution, respectively. The occurrence of waters with long residence times at the step corners points toward the possible role of step dehydration as a rate-limiting factor in calcite crystal growth. Indeed, the different distributions of slow and fast waters along the obtuse and acute steps appear to correlate with the different rates of growth observed for the two types of steps. |
| first_indexed | 2025-11-14T07:49:44Z |
| format | Journal Article |
| id | curtin-20.500.11937-23793 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T07:49:44Z |
| publishDate | 2016 |
| publisher | American Chemical Society |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-237932019-02-19T05:35:05Z Structure and Dynamics of Water at Step Edges on the Calcite {101̅4} Surface De La Pierre, Marco Raiteri, Paolo Gale, Julian The behavior of liquid water around obtuse and acute steps parallel to <4̅41> on the {101̅4} cleavage surface of calcite has been investigated by means of classical molecular dynamics simulations performed with a force-field fitted against thermodynamic properties. Water density maps, radial distribution functions, and water average residence times have been investigated. The structure and dynamics of the first two ordered hydration layers, which have been previously observed for the basal surface of calcite, are found to be disrupted by the presence of the steps over a range of five molecular rows either side of the step edge. Calcium sites along the step top edge can coordinate up to three water molecules, as compared with just the single water that can be adsorbed per calcium ion on the flat surface. Water residence times at calcium sites in the vicinity of the step span greater than 2 orders of magnitude, from tenths to several tens of ns, as compared to 2 and 0.2 ns for the flat surface and a calcium ion in aqueous solution, respectively. The occurrence of waters with long residence times at the step corners points toward the possible role of step dehydration as a rate-limiting factor in calcite crystal growth. Indeed, the different distributions of slow and fast waters along the obtuse and acute steps appear to correlate with the different rates of growth observed for the two types of steps. 2016 Journal Article http://hdl.handle.net/20.500.11937/23793 10.1021/acs.cgd.6b00957 http://purl.org/au-research/grants/arc/FT130100463 http://purl.org/au-research/grants/arc/DP160100677 American Chemical Society fulltext |
| spellingShingle | De La Pierre, Marco Raiteri, Paolo Gale, Julian Structure and Dynamics of Water at Step Edges on the Calcite {101̅4} Surface |
| title | Structure and Dynamics of Water at Step Edges on the Calcite {101̅4} Surface |
| title_full | Structure and Dynamics of Water at Step Edges on the Calcite {101̅4} Surface |
| title_fullStr | Structure and Dynamics of Water at Step Edges on the Calcite {101̅4} Surface |
| title_full_unstemmed | Structure and Dynamics of Water at Step Edges on the Calcite {101̅4} Surface |
| title_short | Structure and Dynamics of Water at Step Edges on the Calcite {101̅4} Surface |
| title_sort | structure and dynamics of water at step edges on the calcite {101̅4} surface |
| url | http://purl.org/au-research/grants/arc/FT130100463 http://purl.org/au-research/grants/arc/FT130100463 http://hdl.handle.net/20.500.11937/23793 |