Calcium peroxide from ambient to high pressures

Literature Information

Publication Date 2015-02-06
DOI 10.1039/C4CP05644B
Impact Factor 3.676
Authors

Joseph R. Nelson, Richard J. Needs, Chris J. Pickard


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Abstract

Structures of calcium peroxide (CaO2) are investigated in the pressure range 0–200 GPa using the ab initio random structure searching (AIRSS) method and density functional theory (DFT) calculations. At 0 GPa, there are several CaO2 structures very close in enthalpy, with the ground-state structure dependent on the choice of exchange–correlation functional. Further stable structures for CaO2 with C2/c, I4/mcm and P21/c symmetries emerge at pressures below 40 GPa. These phases are thermodynamically stable against decomposition into CaO and O2. The stability of CaO2 with respect to decomposition increases with pressure, with peak stability occurring at the CaO B1–B2 phase transition at 65 GPa. Phonon calculations using the quasiharmonic approximation show that CaO2 is a stable oxide of calcium at mantle temperatures and pressures, highlighting a possible role for CaO2 in planetary geochemistry. We sketch the phase diagram for CaO2, and find at least five new stable phases in the pressure–temperature ranges 0 ≤ P ≤ 60 GPa, 0 ≤ T ≤ 600 K, including two new candidates for the zero-pressure ground state structure.

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DOI: 10.1039/C8CP91887B

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

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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