Li2NH晶体结构建模和电子结构的第一性原理研究

于大龙; 陈玉红; 曹一杰; 张材荣

doi:10.7498/aps.59.1991

摘要

基于密度泛函理论的赝势－平面波方法，采用三种模型分别研究Li，N原子对N—H键方位的影响以及N—H键间的相互影响，得到了Li2NH的晶体结构和H原子的占位位置.计算结果表明：Li2NH晶体为层状结构，空间群为P42，晶胞中4个N—H键分为两层，层内N—H键为反平行排列，层间N—H键为垂直排列.态密度和电子局域函数（ELF）分析表明，N—H键呈明显的共价键特性，Li和N—H键呈明显的离子键相互作用.可逆储氢反应Li2<

关键词:

Abstract

The crystal structure and the locations of the hydrogen of lithium imide （Li2NH） are studied by first-principle plane wave pseudopotential method based on the density function theory（DFT）. Three models are used to investigating the effects of the Li, N and nearest-neighbor N—H bonds to N—H bond orientation, respectively. The calculated results show that Li2NH crystal can be described by a layered tetragonal crystal （P42） structure. Four N—H bonds of each conventional cell align in two layers. The two imide groups in the same layer prefer to be antiparallel and the imide groups in the nearest-neighbor layers tend to be vertical. The density of states （DOS） and the electron local function （ELF） analysis show strong ionic interaction between the Li and N—H dimmer, while the bonding between the N and H has covalent character. Our P42 structure of Li2NH crystal yields a hydrogen storage Li2NH2+H2/LiNH2+LiH reaction enthalpy of 69.6 kJ/mol H2 at T=0 K, in good agreement with experimental reports of 66 kJ/mol H2 for this reaction.

Keywords:

作者及机构信息

(1)兰州理工大学,甘肃省有色金属新材料省部共建国家重点实验室，兰州 730050；兰州理工大学理学院，兰州 730050; (2)兰州理工大学理学院，兰州 730050

基金项目: 国家自然科学基金（批准号：10547007）和兰州理工大学优秀青年教师培养计划（批准号：Q200317）资助的课题.

Authors and contacts

(1)兰州理工大学,甘肃省有色金属新材料省部共建国家重点实验室，兰州 730050；兰州理工大学理学院，兰州 730050; (2)兰州理工大学理学院，兰州 730050

参考文献

[1]	［1］Chen P, Xiong Z, Luo J, Lin J, Tan K L 2002 Nature 420 302
[2]	［2］Smith D K, Leider H R 1968 J. Appl. Crystallogr. 1 246
[3]	［3］Jacobs H, Juza R 1972 Z. Anorg. Allg. Chem. 391 271
[4]	［4］Milman V, Winkler B 2001 Z. Kristallogr. 216 99
[5]	［5］Ohoyama K, Nakamori Y, Orimo S, Yamada K 2005 J. Phys. Soc. Jpn. 74 483
[6]	［6］Noritake T, Nozaki H, Aoki M, Towata S, Kitahara G, Nakamori Y, Orimo S 2005 J. Alloys Compd. 393 264
[7]	［7］Balogh M P, Jones C Y, Herbst J F, Hector J, Kundrat M 2006 J. Alloys Compd. 420 326
[8]	［8］Mueller T, Ceder G 2006 Phys. Rev. B 74 134104
[9]	［9］Zhang C J, Dyer M, Alavi A 2005 J. Phys. Chem. B 109 22089
[10]	］Kohn W, Sham L J 1965 Phys. Rev. A 140 1133
[11]	］Payne M C, Teter M P, Allan D C, Arials T A, Joannopoulos J D 1992 Rev. Mod. Phys. 64 1045
[12]	］Magyari-Kpe B, Ozolin V, Wolverton C 2006 Phys. Rev. B 73 220101
[13]	］Tsumuraya T, Shishidou T, Oguchi T 2007 J. Alloys Compd. 446-447 323
[14]	］Soulié J P, Renaudin G, Cerny′ R, Yvon K 2002 J. Alloys Compd. 346 200
[15]	］Hauback B C, Brinks H W, Fjellvag H 2002 J. Alloys Compd. 346 184
[16]	］Chen Y H, Kang L, Zhang C R, Luo Y C, Pu Z S 2008 Acta Phys. Sin. 57 4174 （in Chinese）［陈玉红、康龙、张材荣、罗永春、蒲忠胜 2008 物理学报 57 4174］
[17]	］Yu X, Luo X G, Chen G F, Shen J, Li Y X 2007 Acta Phys. Sin. 56 5366 （in Chinese）［宇霄、罗晓光、陈贵锋、沈俊、李养贤 2007 物理学报 56 5366］
[18]	］Herbst J F, Hector J 2005 Phys. Rev. B 72 125120
[19]	］Gupta M, Gupta R P 2007 J. Alloys Compd. 446-447 319
[20]	］Kojima Y, Kawai Y 2005 J. Alloys Compd. 395 236

施引文献

[1]	［1］Chen P, Xiong Z, Luo J, Lin J, Tan K L 2002 Nature 420 302
[2]	［2］Smith D K, Leider H R 1968 J. Appl. Crystallogr. 1 246
[3]	［3］Jacobs H, Juza R 1972 Z. Anorg. Allg. Chem. 391 271
[4]	［4］Milman V, Winkler B 2001 Z. Kristallogr. 216 99
[5]	［5］Ohoyama K, Nakamori Y, Orimo S, Yamada K 2005 J. Phys. Soc. Jpn. 74 483
[6]	［6］Noritake T, Nozaki H, Aoki M, Towata S, Kitahara G, Nakamori Y, Orimo S 2005 J. Alloys Compd. 393 264
[7]	［7］Balogh M P, Jones C Y, Herbst J F, Hector J, Kundrat M 2006 J. Alloys Compd. 420 326
[8]	［8］Mueller T, Ceder G 2006 Phys. Rev. B 74 134104
[9]	［9］Zhang C J, Dyer M, Alavi A 2005 J. Phys. Chem. B 109 22089
[10]	］Kohn W, Sham L J 1965 Phys. Rev. A 140 1133
[11]	］Payne M C, Teter M P, Allan D C, Arials T A, Joannopoulos J D 1992 Rev. Mod. Phys. 64 1045
[12]	］Magyari-Kpe B, Ozolin V, Wolverton C 2006 Phys. Rev. B 73 220101
[13]	］Tsumuraya T, Shishidou T, Oguchi T 2007 J. Alloys Compd. 446-447 323
[14]	］Soulié J P, Renaudin G, Cerny′ R, Yvon K 2002 J. Alloys Compd. 346 200
[15]	］Hauback B C, Brinks H W, Fjellvag H 2002 J. Alloys Compd. 346 184
[16]	］Chen Y H, Kang L, Zhang C R, Luo Y C, Pu Z S 2008 Acta Phys. Sin. 57 4174 （in Chinese）［陈玉红、康龙、张材荣、罗永春、蒲忠胜 2008 物理学报 57 4174］
[17]	］Yu X, Luo X G, Chen G F, Shen J, Li Y X 2007 Acta Phys. Sin. 56 5366 （in Chinese）［宇霄、罗晓光、陈贵锋、沈俊、李养贤 2007 物理学报 56 5366］
[18]	］Herbst J F, Hector J 2005 Phys. Rev. B 72 125120
[19]	］Gupta M, Gupta R P 2007 J. Alloys Compd. 446-447 319
[20]	］Kojima Y, Kawai Y 2005 J. Alloys Compd. 395 236

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