Beyond the point defect limit: solid solutions, phase diagrams and trace-element partitioning
文献信息
M. Yu. Lavrentiev, N. L. Allan, J. A. Purton
Traditionally disorder in solid oxides has largely been investigated theoretically via classical point defect theory; such methods are not readily extended to solid solutions, liquid phases or grossly non-stoichiometric compounds. In this paper we show how Monte Carlo simulations in the semigrand canonical ensemble, which include the explicit interchange of cations and use configurational bias techniques, are an attractive method for situations involving finite and even high concentrations of defects or foreign atoms. We illustrate our approach with two examples involving CaO: (i) the phase diagram for the system CaO–MgO is calculated for both solid and liquid phases. All the characteristic features are reproduced, including the eutectic point and the regions of liquid–solid coexistence; (ii) the first direct calculation of trace-element partitioning between solid and melt phases. Our techniques take full account of local structural distortion and clustering due to the mismatch between the sizes of the cations involved.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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