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Crystal nucleation and growth presents a significant challenge to molecular simulation, requiring long timescale methods to observe formation of nuclei in an achievable simulation. Various approaches, most notably based on metadynamics and transition path sampling, have been applied to the freezing of various one-component systems, with data on nucleation kinetics computed for only a handful of systems. Other, non-classical nucleation mechanisms present an even greater challenge. For example, the growth of biominerals involves stable pre-nucleation clusters, hydrated amorphous precursors and metastable intermediate crystal phases [1]. At each of these stages, growth can be directed and controlled by the presence of proteins, organic scaffolds and other additives. This talk will review work in which metadynamics simulations have been able to provide some insight into various stages of the biomineralisation process, [2-6] and more recent "brute force" simulations which emphasize the importance of atomistic models which correctly capture the thermodynamics of the water-mineral interface [7]. Finally, future challenges in using these models to calculate the kinetics of multi-stage nucleation and growth processes will be highlighted.
[1] J. H. Harding et al Chem. Rev., 108(11):4823-4854, 2008. [2] D. Quigley and P. M. Rodger. J. Chem. Phys., 128 (22) 221101, 2008. [3] D. Quigley and P. M. Rodger. Mol. Simul., 35(7):613-623, 2009. [4] D. Quigley, et al. J. Chem. Phys., 131(9):094703, 2009. [5] D. Quigley, et al. J. Chem. Phys., 134:044703, 2011. [6] C. L. Freeman, J. H. Harding, D. Quigley, and P. M. Rodger. Angew. Chem., 49(30):5135-5137, 2010. [7] P. Raiteri, J. D. Gale, D. Quigley, and P. M. Rodger. J. Phys. Chem. C., 114(13):5997-6010, 2010. |
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