Thermodynamically Consistent Force Field for Molecular Dynamics Simulations of Alkaline-Earth Carbonates and Their Aqueous Speciation

Raiteri, Paolo; Demichelis, Raffaella; Gale, Julian D.

doi:10.1021/acs.jpcc.5b07532

Cited by 153 publications

(288 citation statements)

References 81 publications

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“…One or two water molecules typically occupy the vacancies at any given time, with exchanges taking place on a nanosecond time scale and the hydration layer structure above the surface is more strongly perturbed compared to the charge neutral substitutions. Over the Mg 2þ /Fe 2þ substitution, the water molecule is at a lower position compared to Ca 2þ in the perfect surface, whereas over Sr 2þ the water molecule is higher, which is in good agreement with the radii of the first solvation shell of Ca, Sr, and Mg ions in solution [27]. For the ½FeOH 2þ substitution, the hydroxide oxygen atom is at a similar lateral position as the water oxygen over Ca in the perfect surface, but at a lower height.…”

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confidence: 73%

Resolving Point Defects in the Hydration Structure of Calcite (10.4) with Three-Dimensional Atomic Force Microscopy

et al. 2018

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It seems natural to assume that defects at mineral surfaces critically influence interfacial processes such as the dissolution and growth of minerals in water. The experimental verification of this claim, however, is challenging and requires real-space methods with utmost spatial resolution, such as atomic force microscopy (AFM). While defects at mineral-water interfaces have been resolved in 2D AFM images before, the perturbation of the surrounding hydration structure has not yet been analyzed experimentally. In this Letter, we demonstrate that point defects on the most stable and naturally abundant calcite (10.4) surface can be resolved using high-resolution 3D AFM-even within the fifth hydration layer. Our analysis of the hydration structure surrounding the point defect shows a perturbation of the hydration with a lateral extent of approximately one unit cell. These experimental results are corroborated by molecular dynamics simulations.

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confidence: 73%

Resolving Point Defects in the Hydration Structure of Calcite (10.4) with Three-Dimensional Atomic Force Microscopy

et al. 2018

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“…Here the COSMO solvation model 32 was used with atomic radii fitted such that the experimental hydration free energies of calcium and carbonate were reproduced. A modified force field was then developed by refitting the calcium-carbonate interaction of an earlier model 33 , such that the energy difference between calcite and the ions in aqueous solution was consistent with the experimental solubility. Starting from the optimised bulk structure of calcite commensurate with this model, a rhombohedral nanoparticle of calcite was cleaved with dimensions of 16 x 16 x 4 atomic rows oriented such the long edges run parallel to either the acute or obtuse step edge directions.…”

Section: Methodsmentioning

confidence: 99%

Predicting crystal growth via a unified kinetic three-dimensional partition model

Anderson

Gebbie-Rayet

Hill

et al. 2017

Nature

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2017) 'Predicting crystal growth via a uni ed kinetic three-dimensional partition model. ', Nature., 544 (7651). pp. 456-459. Further information on publisher's website:https://doi.org/10.1038/nature21684Publisher's copyright statement:Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Understanding and predicting the course of crystal growth is fundamental to the control of functionality in modern materials. Despite investigations for over one hundred years 1-5 it is only recently that the molecular intricacies of these processes have been revealed by scanning probe microscopies 6-8 . In order to bring some order and understanding to this vast amount of new information requires new rules to be developed and tested. To date, because of the complexity and variety of different crystal systems, this has relied on developing models that are usually constrained to one system only 9-11 . Such work is painstakingly slow and will not be able to achieve the wide scope of understanding in order to create a unified model across crystal types and crystal structures. Here we describe a new approach to understand and, in theory, predict the growth of crystals, including the incorporation of defect structures, by simultaneous molecular-scale simulation of crystal habit and surface topology using a unified kinetic 3-D partition model. We exemplify our approach by predicting the crystal growth of a diverse set of crystal types including zeolites, metal-organic frameworks, calcite, urea and L-cystine.By understanding crystal growth at the molecular scale we have the possibility to control crystal habit, crystal size, the elimination or incorporation of defects and the development of intergrowth structures. As crystals are used in technologies from pharmaceuticals to gas storage and separation materials, from optoelectronic devices to heterogeneous catalysts, such understanding is vital. If we take an example of a very complex and yet very important crystal type, that of zeolites 12 which form the backbone of the heterogeneous catalysis industry, then many of the problems that must be addressed in crystal growth can be illustrated. Zeolites are nanoporous materials were the framework of the material is constructed from a strong covalently bonded network of Si -O and Al -O bonds. The pores of the material are filled with water and cations that balance the negative charge on the framework. Crystals of zeolites grow from aqueous solutions at temperatures up to about 230 o C and it is well known from NMR spectroscopy that...

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“…Properties, such as the water solvation free energy, dielectric constant, and structure, are found to be in good agreement with experiment for this water model. 49 On the other hand, the interactions involving BPP are much harder to benchmark due to the lack of experimental data to compare against; quantities such as the solvation free energy of BPP or the BPP−calcium pairing free energy are indeed unknown. Due to the complexity of the molecule, it is currently too expensive to run ab initio calculations in bulk water for a sufficiently long time to obtain benchmark data against which to calibrate the force field.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

Where Is the Most Hydrophobic Region? Benzopurpurine Self-Assembly at the Calcite–Water Interface

et al. 2017

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Control of molecular self-assembly at solid− liquid interfaces is challenging due to the complex interplay between molecule−molecule, molecule−surface, molecule− solvent, surface−solvent, and solvent−solvent interactions. Here, we use in-situ dynamic atomic force microscopy to study the self-assembly of Benzopurpurine 4B into oblong islands with a highly ordered inner structure yet incommensurate with the underlying calcite (10.4) surface. Molecular dynamics and free energy calculations provide insights by showing that Benzopurpurine 4B molecules do not anchor to the surface directly but instead assemble on top of the second hydration layer. This seemingly peculiar behavior was then rationalized by considering that hydrophobic molecules placed atop the second water layer cause the least distortion to the existing hydration structure. Further experiments for the adsorption of Benzopurpurine 4B on other minerals indicate that the specific interfacial water structure on calcite is decisive for rationalizing the self-assembly of Benzopurpurine 4B in this system.

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Thermodynamically Consistent Force Field for Molecular Dynamics Simulations of Alkaline-Earth Carbonates and Their Aqueous Speciation

Cited by 153 publications

References 81 publications

Resolving Point Defects in the Hydration Structure of Calcite (10.4) with Three-Dimensional Atomic Force Microscopy

Resolving Point Defects in the Hydration Structure of Calcite (10.4) with Three-Dimensional Atomic Force Microscopy

Predicting crystal growth via a unified kinetic three-dimensional partition model

Where Is the Most Hydrophobic Region? Benzopurpurine Self-Assembly at the Calcite–Water Interface

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