Stable Calcium Nitrides at Ambient and High Pressures

Zhu, Shuangshuang; Peng, Feng; Liu, Hanyu; Majumdar, Arnab; Gao, Tao; Yao, Yansun

doi:10.1021/acs.inorgchem.6b00948

Stable Calcium Nitrides at Ambient and High Pressures

Journal Article · Mon Jul 18 00:00:00 EDT 2016 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.6b00948· OSTI ID:1388071

Zhu, Shuangshuang ^[1]; Peng, Feng ^[2]; Liu, Hanyu ^[3]; Majumdar, Arnab ^[4]; Gao, Tao ^[1]; Yao, Yansun ^[5]

Sichuan Univ., Chengdu (China). Inst. of Atomic & Molecular Physics
Luoyang Normal Univ., Luoyang(China); Beijing Computational Science Research Center, Beijing (China)
Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
Univ. of Saskatchewan, Saskatoon, SK (Canada)
Univ. of Saskatchewan, Saskatoon, SK (Canada); Canadian Light Sources, Inc., Saskatoon, SK (Canada)

The knowledge of stoichiometries of alkaline-earth metal nitrides, where nitrogen can exist in polynitrogen forms, is of significant interest for understanding nitrogen bonding and its applications in energy storage. For calcium nitrides, there were three known crystalline forms, CaN₂, Ca₂N, and Ca₃N₂, at ambient conditions. In the present study, we demonstrated that there are more stable forms of calcium nitrides than what is already known to exist at ambient and high pressures. Using a global structure searching method, we theoretically explored the phase diagram of CaNx and discovered a series of new compounds in this family. In particular, we found a new CaN phase that is thermodynamically stable at ambient conditions, which may be synthesized using CaN₂ and Ca₂N. Four other stoichiometries, namely, Ca₂N₃, CaN₃, CaN₄, and CaN₅, were shown to be stable under high pressure. The predicted CaN_x compounds contain a rich variety of polynitrogen forms ranging from small molecules (N₂, N₄, N₅, and N₆) to extended chains (N_∞). Because of the large energy difference between the single and triple nitrogen bonds, dissociation of the CaN_x crystals with polynitrogens is expected to be highly exothermic, making them as potential high-energy-density materials.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research in Extreme Environments (EFree)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001057

OSTI ID:: 1388071

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 15 Vol. 55; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (29)

The Vibrational Spectra and Decomposition ofα-Calcium Nitride (α-Ca3N2) and Magnesium Nitride (Mg3N2) Heyns, Anton M.; Prinsloo, Linda C.; Range, Klaus-Jürgen Journal of Solid State Chemistry, Vol. 137, Issue 1 https://doi.org/10.1006/jssc.1997.7672	journal	April 1998
Influence of MgO on the growth of cubic boron nitride using the catalyst Mg3N2 Lorenz, Helmar; Kühne, Ulrich; Hohlfeld, Christian Journal of Materials Science Letters, Vol. 7, Issue 1 https://doi.org/10.1007/BF01729904	journal	January 1988
Charge, bond order and valence in the AB initio SCF theory Mayer, I. Chemical Physics Letters, Vol. 97, Issue 3 https://doi.org/10.1016/0009-2614(83)80005-0	journal	May 1983
Solid state metathesis routes to Group IIIa nitrides : comparison of Li3N, NaN3, Ca3N2 and Mg3N2 as nitriding agents Parkin, I. P.; Nartowski, A. M. Polyhedron, Vol. 17, Issue 16 https://doi.org/10.1016/S0277-5387(97)00454-3	journal	June 1998
CALYPSO: A method for crystal structure prediction Wang, Yanchao; Lv, Jian; Zhu, Li Computer Physics Communications, Vol. 183, Issue 10 https://doi.org/10.1016/j.cpc.2012.05.008	journal	October 2012
Crystalline LiN ₅ Predicted from First-Principles as a Possible High-Energy Material Peng, Feng; Yao, Yansun; Liu, Hanyu The Journal of Physical Chemistry Letters, Vol. 6, Issue 12 https://doi.org/10.1021/acs.jpclett.5b00995	journal	June 2015
Synthesis of Alkaline Earth Diazenides M _AE N ₂ (M _AE = Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure Schneider, Sebastian B.; Frankovsky, Rainer; Schnick, Wolfgang Inorganic Chemistry, Vol. 51, Issue 4 https://doi.org/10.1021/ic2023677	journal	January 2012
Crystal structure of dicalcium nitride Keve, E. T.; Skapski, A. C. Inorganic Chemistry, Vol. 7, Issue 9 https://doi.org/10.1021/ic50067a014	journal	September 1968
Ca₃N₂ and Mg₃N₂: Unpredicted High-Pressure Behavior of Binary Nitrides Braun, Cordula; Börger, Saskia L.; Boyko, Teak D. Journal of the American Chemical Society, Vol. 133, Issue 12, p. 4307-4315 https://doi.org/10.1021/ja106459e	journal	March 2011
Induction of an Aromatic Six-Membered Nitrogen Ring via Cation−π Interaction Duan, Hongxia; Gong, Zhen; Cheng, Jiagao The Journal of Physical Chemistry A, Vol. 110, Issue 44 https://doi.org/10.1021/jp063348a	journal	October 2006
Experimental Determinations of the High-Pressure Crystal Structures of Ca ₃ N ₂ Hao, J.; Li, Y. W.; Wang, J. S. The Journal of Physical Chemistry C, Vol. 114, Issue 39 https://doi.org/10.1021/jp105861y	journal	September 2010
Hidden Thermodynamic Ground State of Calcium Diazenide Wang, Hui; Yao, Yansun; Si, Yanling The Journal of Physical Chemistry C, Vol. 118, Issue 1 https://doi.org/10.1021/jp410281q	journal	December 2013
Density Functional Study of Calcium Nitride: Refined Geometries and Prediction of High-Pressure Phases Römer, S. Rebecca; Schnick, Wolfgang; Kroll, Peter The Journal of Physical Chemistry C, Vol. 113, Issue 7 https://doi.org/10.1021/jp8077002	journal	January 2009
Preparation and characterisation of MgSiN₂ powders Bruls, R. J.; Hintzen, H. T.; Metselaar, R. Journal of Materials Science, Vol. 34, Issue 18, p. 4519-4531 https://doi.org/10.1023/A:1004645407523	journal	January 1999
Experimental and theoretical equation of state of cubic boron nitride Knittle, Elise; Wentzcovitch, Renata M.; Jeanloz, Raymond Nature, Vol. 337, Issue 6205 https://doi.org/10.1038/337349a0	journal	January 1989
The formation of sp3 bonding in compressed BN Meng, Yue; Mao, Ho-kwang; Eng, Peter J. Nature Materials, Vol. 3, Issue 2 https://doi.org/10.1038/nmat1060	journal	January 2004
Single-bonded cubic form of nitrogen Eremets, Mikhail I.; Gavriliuk, Alexander G.; Trojan, Ivan A. Nature Materials, Vol. 3, Issue 8 https://doi.org/10.1038/nmat1146	journal	July 2004
Exotic stable cesium polynitrides at high pressure Peng, Feng; Han, Yunxia; Liu, Hanyu Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep16902	journal	November 2015
Dicalcium nitride, Ca2N—a 2D "excess electron" compound; synthetic routes and crystal chemistry Gregory, Duncan H.; Bowman, Amy; Baker, Charles F. Journal of Materials Chemistry, Vol. 10, Issue 7 https://doi.org/10.1039/b001911i	journal	January 2000
A simple measure of electron localization in atomic and molecular systems Becke, A. D.; Edgecombe, K. E. The Journal of Chemical Physics, Vol. 92, Issue 9 https://doi.org/10.1063/1.458517	journal	May 1990
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Electronic properties of transition-metal nitrides: The group-V and group-VI nitrides VN, NbN, TaN, CrN, MoN, and WN Papaconstantopoulos, D. A.; Pickett, W. E.; Klein, B. M. Physical Review B, Vol. 31, Issue 2 https://doi.org/10.1103/PhysRevB.31.752	journal	January 1985
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Crystal structure prediction via particle-swarm optimization Wang, Yanchao; Lv, Jian; Zhu, Li Physical Review B, Vol. 82, Issue 9 https://doi.org/10.1103/PhysRevB.82.094116	journal	September 2010
Stable xenon nitride at high pressures Peng, Feng; Wang, Yanchao; Wang, Hui Physical Review B, Vol. 92, Issue 9 https://doi.org/10.1103/PhysRevB.92.094104	journal	September 2015
High Energy Density Mixed Polymeric Phase from Carbon Monoxide and Nitrogen Raza, Zamaan; Pickard, Chris J.; Pinilla, Carlos Physical Review Letters, Vol. 111, Issue 23 https://doi.org/10.1103/PhysRevLett.111.235501	journal	December 2013
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Synthesis of AlN/Al Alloy Composites by in situ Reaction between Mg₃N₂ and Aluminum Kobashi, Makoto; Okayama, Norihisa; Choh, Takao Materials Transactions, JIM, Vol. 38, Issue 3 https://doi.org/10.2320/matertrans1989.38.260	journal	January 1997

Cited By (14)

Fe-N system at high pressure reveals a compound featuring polymeric nitrogen chains Bykov, M.; Bykova, E.; Aprilis, G. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05143-2	journal	July 2018
High-Pressure Synthesis of a Nitrogen-Rich Inclusion Compound ReN 8 ⋅ x N 2 with Conjugated Polymeric Nitrogen Chains Bykov, Maxim; Bykova, Elena; Koemets, Egor Angewandte Chemie, Vol. 130, Issue 29 https://doi.org/10.1002/ange.201805152	journal	June 2018
High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf ₄ N ₂₀ ⋅N ₂ , WN ₈ ⋅N ₂ , and Os ₅ N ₂₈ ⋅3 N ₂ with Polymeric Nitrogen Linkers Bykov, Maxim; Chariton, Stella; Bykova, Elena Angewandte Chemie, Vol. 132, Issue 26 https://doi.org/10.1002/ange.202002487	journal	May 2020
High-Pressure Synthesis of a Nitrogen-Rich Inclusion Compound ReN ₈ ⋅ x N ₂ with Conjugated Polymeric Nitrogen Chains Bykov, Maxim; Bykova, Elena; Koemets, Egor Angewandte Chemie International Edition, Vol. 57, Issue 29 https://doi.org/10.1002/anie.201805152	journal	June 2018
High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf ₄ N ₂₀ ⋅N ₂ , WN ₈ ⋅N ₂ , and Os ₅ N ₂₈ ⋅3 N ₂ with Polymeric Nitrogen Linkers Bykov, Maxim; Chariton, Stella; Bykova, Elena Angewandte Chemie International Edition, Vol. 59, Issue 26 https://doi.org/10.1002/anie.202002487	journal	May 2020
Alkaline-earth metal (Mg) polynitrides at high pressure as possible high-energy materials Wei, Shuli; Li, Da; Liu, Zhao Physical Chemistry Chemical Physics, Vol. 19, Issue 13 https://doi.org/10.1039/c6cp08771j	journal	January 2017
Structural phase transition and bonding properties of high-pressure polymeric CaN ₃ Hou, Pugeng; Lian, Lili; Cai, Yongmao RSC Advances, Vol. 8, Issue 8 https://doi.org/10.1039/c7ra11260b	journal	January 2018
Metallic and anti-metallic properties of strongly covalently bonded energetic AlN ₅ nitrides Liu, Zhao; Li, Da; Liu, Yan Physical Chemistry Chemical Physics, Vol. 21, Issue 22 https://doi.org/10.1039/c9cp01723b	journal	January 2019
High-pressure formation of antimony nitrides: a first-principles study Lian, Lili; Liu, Yan; Li, Da RSC Advances, Vol. 10, Issue 5 https://doi.org/10.1039/c9ra09438e	journal	January 2020
Stable zigzag and tripodal all-nitrogen anion N ₄ ⁴⁻ in BeN ₂ Lin, Jiani; Zhu, Zuoqin; Jiang, Qiwen AIP Advances, Vol. 9, Issue 5 https://doi.org/10.1063/1.5098867	journal	May 2019
The reductive coupling of dinitrogen Légaré, Marc-André; Rang, Maximilian; Bélanger-Chabot, Guillaume Science, Vol. 363, Issue 6433 https://doi.org/10.1126/science.aav9593	journal	March 2019
High-pressure synthesis of a nitrogen-rich inclusion compound $ReN_{8}·xN_{2}$ with conjugated polymeric nitrogen chains Bykov, Maxim; Bykova, Elena; Koemets, Egor Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2018-02309	text	January 2018
Fe-N system at high pressure reveals a compound featuring polymeric nitrogen chains Bykov, Maxim; Bykova, E.; Aprilis, G. Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2018-02626	text	January 2018
High‐Pressure Synthesis of Metal–Inorganic Frameworks $Hf{4}N_{2}0 ⋅ N_{2}$ , $WN_{8} ⋅ N_{2}$ , and $Os_{5}N_{28}$ ⋅ 3 $N_{2}$ with Polymeric Nitrogen Linkers Bykov, Maxim; Chariton, Stella; Bykova, Elena Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2021-00175	text	January 2020

Similar Records

Synthesis of Bulk BC8 Silicon Allotrope by Direct Transformation and Reduced-Pressure Chemical Pathways

Journal Article · Tue Aug 16 20:00:00 EDT 2016 · Inorganic Chemistry · OSTI ID:1388105

Exotic stable cesium polynitrides at high pressure

Journal Article · Wed Nov 18 19:00:00 EST 2015 · Scientific Reports · OSTI ID:1241100

Route to high-energy density polymeric nitrogen t-N via He-N compounds

Journal Article · Sun Feb 18 19:00:00 EST 2018 · Nature Communications · OSTI ID:1470638

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
catalysis (heterogeneous)
charge transport
energy storage (including batteries and capacitors)
hydrogen and fuel cells
materials and chemistry by design
mesostructured materials
phonons
solar (photovoltaic)
superconductivity
synthesis (novel materials)
thermoelectric

Stable Calcium Nitrides at Ambient and High Pressures

Citation Formats

References (29)

Cited By (14)

Similar Records

Related Subjects