Electro-Crystallisation at Liquid Liquid Interfaces

Soft interfaces are ubiquitous in our lives and they play fundamental roles in regulating biological, industrial geochemical and processes, such as protecting the cells from the outside environment, then extraction of heavy metals from solution or the growth of minerals. The project aims to understand how minerals forms at the interface between two immiscible solutions, with and without the aid of an external electric field. In this process, positive and negative ions are kept separate in the two immiscible liquids and get into contact at the interface where they can form ordered arrangements and grow into macroscopic size crystals.

Principal investigator

Paolo Raiteri p.raiteri@curtin.edu.au
Magnifying glass

Area of science

Chemistry, Geochemistry

Systems used

Magnus, Zeus, Nimbus, Topaz, Managed Storage, Visualisation

Applications used

Lammps, openMM, VMD,Tinker HP
Partner Institution: Curtin University| Project Code: pawsey0185

The Challenge

Soft interfaces are difficult to characterise experimentally due their mobile and ever changing structure and there are only a few experimental techniques that can provide insight into the structure and thickness of the interface region. However, these techniques cannot provide atomic resolution and can only provide average properties over thicknesses that are muck larger than the interface region itself

The Solution

All-atom molecular dynamics simulations are an ideal tool to investigate these system as they can provide sub-nanometer and picosecond resolution on the structure and dynamic of the interface. The fundamental and often most time consuming step to obtain reliable and quantitatively accurate results from computer simulations in the development and validation of the models used to describe the atomic interactions. Particularly challenging is also the use external electric field as it breaks the system symmetry and requires much larger simulation cells.

The Outcome

A key step forward to accurately describe the ion association in the presence of external electric field is to use polarisable atomistic models which can capture the response of the electrons in a mean field way. These are particularly time consuming simulations but they can run efficiently on GPUs. Part of the model development was done on Magnus and most of the production runs were done on Athena/Zeus/Topaz with Zeus also used for data analysis.

List of Publications

(1] N. A. Garcia, R. I. Malini, C. L. Freeman, R. Demichelis, P. Raiteri, N. A. J. M. Sommerdijk, J. H. Harding, and J. D. Gale
Simulation of Calcium Phosphate Prenucleation Clusters in Aqueous Solution: Association Be- yond Ion Pairing.
Crystal Growth & Design; 19 (11), 6422–6430 (2019). doi: {10.1021/acs.cgd.9b00889}, [Cited by 0]

[2] W. Jiang, D. Athanasiadou, S. Zhang, R. Demichelis, K. B. Koziara, P. Raiteri, V. Nelea, W. Mi, J.-A. Ma, J. D. Gale, and M. D. McKee
Homochirality in Biomineral Suprastructures Induced by Assembly Of Single-Enantiomer Amino Acids From a Nonracemic Mixture.
Nature Communications; 10, 2318 (2019).
doi: {10.1038/s41467-019-10383-x}, [Cited by 1]

[3] B.-Q. Lu, N. A. Garcia, D. M. Chevrier, P. Zhang, P. Raiteri, J. D. Gale, and D. Gebauer Short-Range Structure of Amorphous Calcium Hydrogen Phosphate.
Crystal Growth & Design; 19 (5), 3030–3038 (2019).
doi: {10.1021/acs.cgd.9b00274}, [Cited by 4]

[4] C. Moir, L. Lue, J. D. Gale, P. Raiteri, and M. N. Bannerman Anomalous Heat Transport in Binary Hard-Sphere Gases. Physical Review E; 99 (3), 030102 (2019).
doi: {10.1103/PhysRevE.99.030102}, [Cited by 0]

[5] B. Reischl, P. Raiteri, J. D. Gale, and A. L. Rohl
Atomistic Simulation of Atomic Force Microscopy Imaging of Hydration Layers on Calcite, Dolomite, and Magnesite Surfaces.
Journal of Physical Chemistry C; 123 (24), 14985–14992 (2019).
doi: {10.1021/acs.jpcc.9b00939}, [Cited by 1]

[6] A. Silvestri, E. Ataman, A. Budi, S. L. S. Stipp, J. D. Gale, and P. Raiteri
Wetting Properties of the CO2 -Water-Calcite System via Molecular Simulations: Shape and Size Effects.
Langmuir; 35 (50), 16669–16678 (2019).
doi: {10.1021/acs.langmuir.9b02881}, [Cited by 0]

[7] T. M. Stawski, A. E. S. Van Driessche, R. Besselink, E. H. Byrne, P. Raiteri, J. D. Gale, and L. G. Benning
The Structure of CaSO4 Nanorods: The Precursor of Gypsum. Journal of Physical Chemistry C; 123 (37), 23151–23158 (2019). doi: {10.1021/acs.jpcc.9b04268}, [Cited by 2]

[8] N. S. L. Tan, P. V. Simpson, G. L. Nealon, A. N. Sobolev, P. Raiteri, M. Massi, M. I. Ogden, and A. B. Lowe
Rhodium(I)-α-Phenylvinylfluorenyl Complexes: Synthesis, Characterization, and Evaluation as Initiators in the Stereospecific Polymerization of Phenylacetylene.
European Journal of Inorganic Chemistry; (5), 592–601 (2019).
doi: {10.1002/ejic.201801411}, [Cited by 3].

Atomistic representation of the water/1,2-Dichloroethane interface. The water is shown as a blue surface, carbon and chlorine atoms are represented in black and green, respectively. All hydrogens have been removed and only the 1,2-Dichloroethane in contact with the water surface are shown for clarity