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Recent studies have shown that introducing metal elements into nitrogen matrix can induce more stable poly-nitrogen structures than the pure nitrogen phase due to the ionic interaction between metal elements and nitrogen matrix. Many types of poly-nitrogen structures have been reported by using the alkaline earth metal elements (M = Be, Mg, Ca, Sr, Ba) as the coordinate elements. For example, the one-dimensional (1D) infinite armchair poly-nitrogen chain (N∞) structure and N6 ring structure are obtained for the MN4 and MN3 chemical stoichiometry, respectively. Interestingly, the stabilities of theses MNx structures are enhanced 2–3 times compared with that of the pure nitrogen. Therefore, exploring the novel and stable poly-nitrogen structure by introducing alkaline earth metal elements under high pressure is a great significant job. As an alkaline earth element, Ca is abundant in the earth. Its ionization energy (I1 = 590 kJ/mol) is far lower than that of Be (900 kJ/mol) and Mg (738 kJ/mol), which means that Ca can form calcium nitrides more easily. Zhu et al. (Zhu S, Peng F, Liu H, Majumdar A, Gao T, Yao Y 2016Inorg. Chem. 55 7550) proposed that the Ca-N system can obtain poly-nitrogen structures under high pressure, such as CaN4 structure with armchair nitrogen chain, CaN5 and CaN3 consisting of pentazolate “N5” and benzene-like “N6” anions. These poly-nitrogen structures have potential applications in the field of high energy density materials. Here, we report the prediction of Ca-N system at 100 GPa by using particle swarm optimization algorithm technique for crystal structure prediction. A new thermal stable phase with P 21/c-Ca5N4 space group is found at 100 GPa, which enriches the phase of Ca-N system under high pressure. The dynamic stability and mechanical stability of new phase are confirmed by phono dispersion spectrum and elastic constant calculations. The electron localization function analysis shows that the nitrogen atoms in P 21/c-Ca5N4 are bonded by N—N single bond and electron transfer from Ca atom to N atom enables Ca5N4 to serve as an ionic-bonding interaction structure. Band structure calculation shows that the Ca5N4 has a semiconductor structure with a direct band gap of 1.447 eV. The PDOS calculation shows the valence band near Fermi energy is mainly contributed by N_p electrons, while the conduction band is mainly contributed by Ca_d electrons, indicating that electrons are transferred from Ca atom to N atom. Bader calculation shows that each N atom obtains 1.26e from Ca atom in P 21/c-Ca5N4. The Raman spectrum and X-ray diffraction spectrum are calculated and detailed Raman vibration modes are identified, which provides theoretical guidance for experimental synthesis.
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Keywords:
- high pressure /
- alkaline earth metal /
- calcium nitrides
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图 1 100 GPa下Ca-N体系落在凸包图上热力学稳定的各比例
Figure 1. Stable phases on the convex hulls of Ca-N system at 100 GPa.
图 2 100 GPa下预测得到的Ca5N4晶体结构图((a))及多面体单元结构((b), (c))
Figure 2. Crystalline structure of the predicted stable Ca5N4: (a) P 21/c phase at 100 GPa; (b), (c) he polyhedron units of Ca5N4.
图 3 P 21/c相在100 GPa下的声子色散曲线图
Figure 3. Phonon dispersion curves of P 21/c phase at 100 GPa
图 4 P 21/c-Ca5N4结构在100 GPa下的二维ELF图
Figure 4. Cross-sections of electron local function of P 21/c-Ca5N4 at 100 GPa.
图 5 P 21/c-Ca5N4在100 GPa下的电子能带结构图和PDOS
Figure 5. Band structure and projected density of states of P 21/c-Ca5N4 at 100 GPa, respectively.
图 6 P 21/c-Ca5N4在100 GPa下的拉曼光谱
Figure 6. Raman spectrum of P 21/c-Ca5N4 at 100 GPa.
图 7 P 21/c-Ca5N4在100 GPa下的XRD图谱
Figure 7. The X-ray diffraction spectrum of P 21/c-Ca5N4 at 100 GPa.
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[1] Pickard C J, Needs R J 2009 Phys. Rev. Lett. 102 125702
Google Scholar
[2] Erba A, Maschio L, Pisani C, Casassa S 2011 Phys. Rev. B 84 012101
Google Scholar
[3] Hirshberg B, Gerber R B, Krylov A I 2014 Nat. Chem. 6 52
Google Scholar
[4] Özçelik V O, Aktürk O Ü, Durgun E, Ciraci S 2015 Phys. Rev. B 92 125420
Google Scholar
[5] Plašienka D, Martoňák R 2015 J. Chem. Phys. 142 094505
Google Scholar
[6] Yakub L N 2016 Low Temp. Phys. 42 1
Google Scholar
[7] Martin R M, Needs R J 1986 Phys. Rev. B 34 5082
Google Scholar
[8] Mailhiot C, Yang L H, McMahan A K 1992 Phys. Rev. B 46 14419
Google Scholar
[9] Wang X, Wang Y, Miao M, Zhong X, Lv J, Cui T, Li J, Chen L, Pickard C J, Ma Y 2012 Phys. Rev. Lett. 109 175502
Google Scholar
[10] Ma Y, Oganov A R, Li Z, Xie Y, Kotakoski J 2009 Phys. Rev. Lett. 102 065501
Google Scholar
[11] Bondarchuk S V, Minaev B F 2017 Comput. Mater. Sci. 133 122
Google Scholar
[12] Eremets M I, Gavriliuk A G, Trojan I A, Dzivenko D A, Boehler R 2004 Nat. Mater. 3 558
Google Scholar
[13] Tomasino D, Kim M, Smith J, Yoo C S 2014 Phys. Rev. Lett. 113 205502
Google Scholar
[14] Zhao J F, Li N, Li Q S 2003 Theor. Chem. Acc. 110 10
Google Scholar
[15] Steele B A, Oleynik I I 2016 Chem. Phys.Lett. 643 21
Google Scholar
[16] Zhang M, Yin K, Zhang X, Wang H, Li Q, Wu Z 2013 Solid State Commun. 161 13
Google Scholar
[17] Peng F, Yao Y, Liu H, Ma Y 2015 J. Phys. Chem. Lett. 6 2363
Google Scholar
[18] Zhang J, Zeng Z, Lin H Q, Li Y L 2015 Sci. Rep. 4 4358
Google Scholar
[19] Wang X, Li J, Zhu H, Chen L, Lin H 2014 J. Chem. Phys. 141 044717
Google Scholar
[20] Williams A S, Steele B A, Oleynik I I 2017 J. Chem. Phys. 147 234701
Google Scholar
[21] Wei S, Li D, Liu Z, Wang W, Tian F, Bao K, Duan D, Liu B, Cui T 2017 J. Phys. Chem. C 121 9766
Google Scholar
[22] Yu S, Huang B, Zeng Q, Oganov A R, Zhang L, Frapper G 2017 J. Phys. Chem. C 121 11037
Google Scholar
[23] Wei S, Li D, Liu Z, Li X, Tian F, Duan D, Liu B, Cui T 2017 Phys. Chem. Chem. Phys. 19 9246
Google Scholar
[24] Hou P, Lian L, Cai Y, Liu B, Wang B, Wei S, Li D 2018 RSC Adv. 8 4314
Google Scholar
[25] Braun C, Börger S L, Boyko T D, Miehe G, Ehrenberg H, Höhn P, Moewes A, Schnick W 2011 J. Am. Chem. Soc. 133 4307
Google Scholar
[26] Hao J, Li Y, Wang J, Ma C, Huang L, Liu R, Cui Q, Zou G, Liu J, Li X 2010 J. Phys. Chem. C 114 16750
Google Scholar
[27] Römer S R, Schnick W, Kroll P 2009 J. Phys. Chem. C 113 2943
Google Scholar
[28] Gregory D H, Bowman A, Baker C F, Weston D P 2000 J. Mater. Chem. 10 1635
Google Scholar
[29] Zhu S, Peng F, Liu H, Majumdar A, Gao T, Yao Y 2016 Inorg. Chem. 55 7550
Google Scholar
[30] Dong X, Oganov A R, Goncharov A F, Stavrou E, Lobanov S, Saleh G, Qian G R, Zhu Q, Gatti C, Deringer V L, Dronskowski R, Zhou X F, Prakapenka V B, Konôpková Z, Popov I A, Boldyrev A I, Wang H T 2017 Nat. Chem. 9 440
Google Scholar
[31] Ma Y, Eremets M, Oganov A R, Xie Y, Trojan I, Medvedev S, Lyakhov A O, Valle M, Prakapenka V 2009 Nature 458 182
Google Scholar
[32] Einaga M, Sakata M, Ishikawa T, Shimizu K, Eremets M I, Drozdov A P, Troyan I A, Hirao N, Ohishi Y 2016 Nat. Phys. 12 835
Google Scholar
[33] Wang Y, Lv J, Zhu L, Ma Y 2012 Comput. Phys. Commun. 183 2063
Google Scholar
[34] Kresse G, Furthmüller J 1996 Phys. Rev. B 54 11169
Google Scholar
[35] Chaput L, Togo A, Tanaka I, Hug G 2011 Phys. Rev. B 84 094302
Google Scholar
[36] Henkelman G, Arnaldsson A, Jónsson H 2006 Comput. Mater. Sci. 36 354
Google Scholar
[37] Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865
Google Scholar
[38] Hammer B, Hansen L B, Nørskov J K 1999 Phys. Rev. B 59 7413
Google Scholar
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