Low-temperature formation of cubic β-PbF2: precursor-based synthesis and first-principles phase stability study

Literature Information

Publication Date 2011-02-21
DOI 10.1039/C0CP01758B
Impact Factor 3.676
Authors

Christoph Erk, Lukas Hammerschmidt, Dirk Andrae, Beate Paulus, Sabine Schlecht


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Abstract

A precursor-based approach to the cubic β-phase of PbF2 was developed and allowed the preparation of this high-temperature phase well below the temperature for transition from the orthorhombic α- to the cubic β-phase. The formation of β-PbF2 from the molecular precursors Pb[Se(C6H2(CF3)3)]2 and Pb(C6H2(CF3)3)2 is facilitated by the presence of several short Pb⋯F contacts in these molecules. The cubic form of PbF2 was obtained as macroscopic crystals as well as nanoparticulate powder. Its formation at relatively low temperature suggested a theoretical re-investigation of the phase stabilities of the two polymorphs. The theoretical results from the Kohn–Sham density functional theory indicate that the energy content for the β-phase is slightly lower than the one for the α-phase, by 0.5–1.7 kJ mol−1 depending on the density functional used (zero-point vibrational energy correction included).

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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