(432d) The Role of Water in the Growth of NaCl Crystals

Crystal habits are influenced by characteristics of solutes and also by the solvent during crystallization [1]. Numerous studies explore how crystal shape depends on characteristics of the solute and interactions between the solvent and crystal facets [2]. However, several experiments and simulations have implicated desolvation barriers in the rate limiting steps for crystal growth [3-5]. Understanding these kinetic barriers is critical for accurate models of crystal growth. We employ simulation methods for rare events and mechanistic hypothesis testing [6] to understand the ion-desolvation process during attachment to a growing NaCl crystal. We calculate the rate of ion attachment at kink sites to predict growth rates and crystal shapes. We also discuss possible extensions of our findings to other crystals, such as calcium carbonate.

[1]  M.A. Lovette, A.R. Browning, D.W. Griffin, J.P. Sizemore, R.C. Snyder, M.F. Doherty, Ind. Eng. Chem. Res. 2008, 47, 9812-9833.

[2]  S.H. Kim, P. Dandekar, M.A. Lovette, M.F. Doherty, Cryst. Growth Des. 2014, 14, 2460-2467.

[3]  P.G. Vekilov, Cryst. Growth Des. 2007, 7, 2796-2810.

[4]  A.G. Stack, P. Raiteri, J.D. Gale, J. Am. Chem. Soc. 2012, 134, 11-14.

[5]  S. Piana, F. Jones, J.D. Gale, J. Am. Chem. Soc. 2006, 128, 13568-13574.

[6]  B. Peters, Mol. Simulat. 2010, 36, 1265-1281.