A reactive force field for lithium-aluminum silicates with applications to eucryptite phases

B Narayanan and ACT van Duin and BB Kappes and IE Reimanis and CV Ciobanu, MODELLING AND SIMULATION IN MATERIALS SCIENCE AND ENGINEERING, 20, 015002 (2012).

DOI: 10.1088/0965-0393/20/1/015002

We have parameterized a reactive force field (ReaxFF) for lithium- aluminum silicates using density functional theory (DFT) calculations of structural properties of a number of bulk phase oxides, silicates and aluminates, as well as of several representative clusters. The force field parameters optimized in this study were found to predict lattice parameters and heats of formation of selected condensed phases in excellent agreement with previous DFT calculations and with experiments. We have used the newly developed force field to study the eucryptite phases in terms of their thermodynamic stability and their elastic properties. We have found that (a) these ReaxFF parameters predict the correct order of stability of the three crystalline polymorphs of eucryptite, alpha, beta and gamma, and (b) that upon indentation, a new phase appears at applied pressures >= 7 GPa. The high-pressure phase obtained upon indentation is amorphous, as illustrated by the radial distribution functions calculated for different pairs of elements. In terms of elastic properties analysis, we have determined the elements of the stiffness tensor for alpha- and beta-eucryptite at the level of ReaxFF, and discussed the elastic anisotropy of these two polymorphs. Polycrystalline average properties of these eucryptite phases are also reported to serve as ReaxFF predictions of their elastic moduli (in the case of alpha-eucryptite), or as tests against values known from experiments or DFT calculations (beta-eucrypite). The ReaxFF potential reported here can also describe well single-species systems (e.g. Li- metal, Al-metal and condensed phases of silicon), which makes it suitable for investigating structure and properties of suboxides, atomic-scale mechanisms responsible for phase transformations, as well as oxidation-reduction reactions.

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