The low coordination number of nitrogen in hard tungsten nitrides: a first-principles study
文献信息
Zhonglong Zhao, Kuo Bao, Defang Duan, Fubo Tian, Yanping Huang, Hongyu Yu, Yunxian Liu, Bingbing Liu, Tian Cui
Tungsten–nitrogen (W–N) compounds are studied via a combination of first-principles calculations and variable-composition evolutionary structure searches. New candidate ground states and high-pressure phases at 3 : 2, 1 : 1, and 5 : 6 compositions are uncovered and established for possible synthesis. We found that the structures in 4/5-fold N coordination (i.e., NbO–WN and W5N6) are more favoured for the W–N system at low-pressures compared with the conventional 6-fold phases (rs-WN and δ-WN). We attribute the low N coordination feature of W–N ground states to the enhanced W 5d–N 2p orbital hybridization and strong covalent W–N bonding, which involves the full-filling of W–N bonding and antibonding states and can remarkably improve the mechanical strength and hardness. These findings not only clarify the phase diagram of the W–N system, but also shed light on the correlations of hardness with microscopic crystal and electronic structures.
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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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