Molecular dynamics investigation of the disordered crystal structure of hexagonal LiBH4

Literature Information

Publication Date 2013-01-29
DOI 10.1039/C3CP44520H
Impact Factor 3.676
Authors

Keith Refson


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Abstract

The crystal structure of the hexagonal phase of solid lithium borohydride (LiBH4) is studied by ab initio molecular dynamics simulations of both the low and high-temperature phases. A temperature range of 200–535 K is simulated with the aim of characterising the disorder in the high-temperature structure in detail. The mechanism and kinetics of the reorientational motion of the borohydride units (BH4−) are determined and are consistent with published neutron scattering experiments; it is found that rotational diffusivity increases by an order of magnitude at the phase transition temperature. The average equilibrium orientation is characterised by a broad distribution of orientations, and reorientational jumps do not occur between sharply defined orientations. In addition, split positions with partial occupancy for the lithium and boron atoms are found (in agreement with previous theoretical studies), which, together with the disordered BH4− orientational distribution in equilibrium, lead to the conclusion that the correct crystallographic space group of the high-temperature phase is P63/mmc rather than P63mc.

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DOI: 10.1039/D0TB90138E

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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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