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Julian D Gale

Publications and source records attributed to Julian D Gale.

12 recordsLinked to original sources
PubMed2006

Assisted desolvation as a key kinetic step for crystal growth.

The crystallization of materials from a supersaturated solution is a fundamental chemical process. Although several very successful models that provide a qualitative understanding of the crystal growth process exist, in most cases the atomistic detail of crystal growth is not fully understood. In this work, molecular dynamics simulations of the morphologically most important surfaces of barite in contact with a supersaturated solution have been performed. The simulations show that an ordered and tightly bound layer of water molecules is present on the crystal surface. The approach of an ion to the surface requires desolvation of both the surface and the ion itself leading to an activated process that is rate limiting for two-dimensional nucleation to occur. However, desolvation on specific surfaces can be assisted by anions adsorbed on the crystal surface. This hypothesis, corroborated by crystallization and scanning electron microscopy studies, allows the rationalization of the morphology of barite crystals grown at different supersaturations.

Journal Article↗
PubMed2005

Simulating micrometre-scale crystal growth from solution.

Understanding crystal growth is essential for controlling the crystallization used in industrial separation and purification processes. Because solids interact through their surfaces, crystal shape can influence both chemical and physical properties. The thermodynamic morphology can readily be predicted, but most particle shapes are actually controlled by the kinetics of the atomic growth processes through which assembly occurs. Here we study the urea-solvent interface at the nanometre scale and report kinetic Monte Carlo simulations of the micrometre-scale three-dimensional growth of urea crystals. These simulations accurately reproduce experimentally observed crystal growth. Unlike previous models of crystal growth, no assumption is made that the morphology can be constructed from the results for independently growing surfaces or from an a priori specification of surface defect concentration. This approach offers insights into the role of the solvent, the degree of supersaturation, and the contribution that extended defects (such as screw dislocations) make to crystal growth. It also connects observations made at the nanometre scale, through in situ atomic force microscopy, with those made at the macroscopic level. If extended to include additives, the technique could lead to the computer-aided design of crystals.

Journal Article↗
PubMed2005

The interaction of dolomite surfaces with metal impurities: a computer simulation study.

This study investigates the behaviour of selected, morphologically important surfaces of dolomite (CaMg(CO3)2), using computational modelling techniques. Interatomic potential methods have been used to examine impurity substitution at cationic sites in these surfaces. Environmentally prevalent cations were studied to this end, namely Ni2+, Co2+, Zn2+, Fe2+, Mn2+ and Cd2+, all of which are also found as end-member carbonate minerals. Solid-solution substitution was investigated and showed that Cd and Mn will substitute from their end-member carbonate phase at either dolomite cation site. Mn is found to preferentially substitute at Mg sites, in agreement with experimental findings. For Ni2+, Co2+ and Zn2+, the magnitude of substitution energies is approximately equal for all surfaces, with the exception of the (1014) surface. However, for the larger cations, a far greater disparity in substitution energies is observed. At a stepped surface, analogous substitutions were performed and it was found that substitution energies for all impurity cations were reduced, indicating that uptake is more viable during growth. The predominant surface, the (1014), was solvated with a monolayer of water in order to investigate the influence of hydration on substitution energetics. The addition of water changes the relative preference for substitution of the different cations. Under aqueous conditions, the substitution energy is determined by three competing factors, the relative importance of which cannot be predicted without this type of computational investigation.

Calcium Carbonate↗
PubMed2005

Atomic scale modelling of the cores of dislocations in complex materials part 1: methodology.

Dislocations influence many properties of crystalline solids, including plastic deformation, growth and dissolution, diffusion and the formation of polytypes. Some of these processes can be described using continuum methods but this approach fails when a description of the structure of the core is required. To progress in these types of problems, an atomic scale model is essential. So far, atomic scale modelling of the cores of dislocations has been limited to systems with rather simple crystal structures. In this article, we describe modifications to current methodology, which have been used for strongly ionic materials with simple structures. These modifications permit the study of dislocation cores in more structurally complex materials.

Biomedical Engineering↗
PubMed2005

Atomic scale modelling of the cores of dislocations in complex materials part 2: applications.

In an accompanying article, we have described a methodology for the simulation of dislocations in structurally complex materials. We illustrate the applicability of this method through studies of screw dislocations in a structurally simple ionic ceramic (MgO), a molecular ionic mineral (forsterite, Mg2SiO4), a semi-ionic zeolite (siliceous zeolite A) and a covalent molecular crystalline material (the pharmaceutical, orthorhombic paracetamol-II). We focus on the extent of relaxation and the structure of the dislocation cores and comment on similarities and points of disparity between these materials. It is found that the magnitude of the relaxation varies from material to material and does not simply correlate with the magnitude of the principal elastic constants in an easily predictable fashion, or with the size of the cohesive lattice energy or length of the Burgers vector, which emphasises the need to model the non-linear forces and atomic structure of the core.

Acetaminophen↗
PubMed2005

Understanding the barriers to crystal growth: dynamical simulation of the dissolution and growth of urea from aqueous solution.

Both the dissolution and growth of a molecular crystalline material, urea, has been studied using dynamical atomistic simulation. The kinetic steps of dissolution and growth are clearly identified, and the activation energies for each possible step are calculated. Our molecular dynamics simulations indicate that crystal growth on the [001] face is characterized by a nucleation and growth mechanism. Nucleation on the [001] urea crystal face is predicted to occur at a very high rate, followed by rapid propagation of the steps. The rate-limiting step for crystallization is actually found to be the removal of surface defects, rather than the initial formation of the next surface layer. Through kinetic Monte Carlo modeling of the surface growth, it is found that this crystal face evolves via a rough surface topography, rather than a clean layer-by-layer mechanism.

Journal Article↗
PubMed2004

Predicting the structure of screw dislocations in nanoporous materials.

Extended microscale crystal defects, including dislocations and stacking faults, can radically alter the properties of technologically important materials. Determining the atomic structure and the influence of defects on properties remains a major experimental and computational challenge. Using a newly developed simulation technique, the structure of the 1/2a <100> screw dislocation in nanoporous zeolite A has been modelled. The predicted channel structure has a spiral form that resembles a nanoscale corkscrew. Our findings suggest that the dislocation will enhance the transport of molecules from the surface to the interior of the crystal while retarding transport parallel to the surface. Crucially, the dislocation creates an activated, locally chiral environment that may have enantioselective applications. These predictions highlight the influence that microscale defects have on the properties of structurally complex materials, in addition to their pivotal role in crystal growth.

Manufactured Materials↗
PubMed2004

An approach to developing a force field for molecular simulation of martensitic phase transitions between phases with subtle differences in energy and structure.

d,l-Norleucine is one of only a few molecules whose crystals exhibit a martensitic or displacive-type phase transformation where the emerging phase shows a topotaxial relationship with the parent phase. The molecular mechanism for such phase transformations, particularly in molecular crystals, is not well understood. Crystalline phases that exhibit displacive phase transitions tend to be very similar in structure and energy. Consequently, the development of a force field for such phases is challenging as the phase behavior is determined by subtle differences in their lattice energies and entropies. We report an approach for developing a force field for such phases with an application to d,l-norleucine. The proposed procedure includes calculation of the phase diagram of the crystalline phases as a function of temperature to identify the best force field. d,l-Norleucine also presents an additional problem since in the solid state it exists as a zwitterion that is unstable in vacuo and therefore cannot be characterized using high-level ab initio calculations in the gas phase. However, a stable zwitterion could be obtained using Onsager's reaction-field continuum model for a solvent (SCRF) using both Hartree-Fock and density functional theory. A number of force fields and the various sets of partial charges obtained from the SCRF calculations were screened for their ability to reproduce the crystal structures of the two known phases, alpha and beta, of d,l-norleucine. Selected parameter sets were then employed in free energy minimizations to identify the best set on the basis of a correct prediction of the alpha-beta phase transition. The Williams' nonbonded parameters combined with partial charges from SCRF-Polarized Continuum Model calculation were found to reproduce the structures of the phases accurately and also maintained their stability in extended molecular dynamics simulations in the Parrinello-Rahman constant stress ensemble. Moreover, we were also able to successfully simulate the phase transformation of the beta- to the alpha-phase. The identified force field should enable detailed studies of the phase transformations exhibited by crystals of d,l-norleucine and hence enhance our understanding of martensitic-type transformations in molecular crystals.

Computer Simulation↗
PubMed2002

Framework stability of nanoporous inorganic structures upon template extraction and calcination: a theoretical study of gallophosphate polymorphs.

A systematic computational study of gallophosphates was undertaken. First, lattice energy minimization calculations using a formal-charge shell model potential have been carried out on a series of hypothetical gallium phosphates derived from their metallogallophosphate, aluminophosphate, or aluminosilicate analogues through atomic substitution. The minimized structures show the typical features in terms of bond angles and distances as expected in zeolitic gallophosphates. Second, the crystal structures of several gallophosphates in their calcined forms have been predicted, using for each compound lattice energy minimization and an initial model derived from its as-synthesized templated form. All the modified structures thus have the same GaPO(4) composition. The lattice energies of all the simulated gallophosphate structures were compared to that of GaPO(4)-quartz as a reference structure. Interestingly, among all predicted calcined structures, various zeolitic topologies were found. The study of the energetics of these zeotypic structures showed a linear dependence of lattice energy upon density. Strikingly, a few simulated structures showed unrealistic structural features, such as important framework distortions, often associated with the occurrence of a hexameric unit in the original as-synthesized structures. Also, those gallophosphates with structural faults were found in the upper part of the energy/density plot. To address the validity of our force field calculations in these special cases, first principles calculations were undertaken on ULM-4, chosen as a typical representative structure. Indeed, the qualitative agreement found between our results and those obtained with the nonlocal density functional theory demonstrates the robustness of our force field. Further minimization also showed that the inclusion of polarizability is crucial for yielding results comparable with those obtained using first principles methods.

Journal Article↗
PubMed2002

Theoretical and experimental investigations on the morphology of pharmaceutical crystals.

We investigated the morphologies of three polymorphs of 1,3-di(cyclopropylmethyl)-8-aminoxanthine, a compound of pharmaceutical importance. We compared the experimental morphologies with those predicted by theoretical methods. We also predicted the elastic constants of the three polymorphs. These results are used to help assess the stabilities of the three polymorphs and compare the abilities of theoretical methods to reproduce experimental morphologies.

Computer Simulation↗