Structural Stability, Electronic Structure and Mechanical Properties of Li-N-H System

doi:10.1007/s40195-015-0231-y

Abstract

Abstract:

Ab initio calculations are performed to investigate the ground state properties, structural phase transition, electronic structure and mechanical properties of lithium nitride (Li₃N), lithium imide (Li₂NH) and lithium amide (LiNH₂). The computed ground state properties like equilibrium lattice constant, cell volume, valence electron density, cohesive energy, bulk modulus and its derivatives are in good agreement with available experimental data. The structural phase transitions from α-P6/mmm to β-P6₃/mmc phase at a pressure of 17.5 GPa in Li₃N and cubic (Fm3m) to hexagonal (P6₃/mmc) phase at a pressure of 102 GPa in lithium imide (Li₂NH) are observed. A new high pressure hexagonal (P6₃/mmc) phase is predicted for Li₂NH. Electronic structure reveals that Li₃N and LiNH₂ are semiconductors, whereas Li₂NH is an insulator. The calculated elastic constants indicate that these materials are mechanically stable at ambient condition.

Key words: Ab initio calculations, Crystal structure, Phase transition, Electronic structure, Mechanical properties

Ratnavelu Rajeswarapalanichamy, Manoharan Santhosh, Ganesapandian Sudhapriyanga, Shanmugam Kanagaprabha, Kombaih Iyakutti. Structural Stability, Electronic Structure and Mechanical Properties of Li-N-H System[J]. Acta Metallurgica Sinica (English Letters), 2015, 28(5): 550-558.

Figures/Tables 13

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Space group	a	c	V₀	ρ	E_coh	B₀	B ′ 0
(P6/mmm)	3.641, 3.600^a, 3.6413^b, 3.534^c, 3.508^d, 3.648^e	3.846, 3.840^a, 3.823^b, 3.772^c, 3.745^d, 3.875^e	45.08	0.1774	8.838084	69.17, 63.90^a, 58.90^c, 61.00^d	3.815, 4.000^d, 3.800^c, 3.700^d
(P6₃/mmc)	3.485, 3.558^b, 3.445^c, 3.418^d, 3.552^e	6.228, 6.250^b, 6.148^c, 6.100^d, 6.310^e	67.30	0.1188	6.756029	86.5, 98.0^a, 74.5^c, 78.2^d	3.421, 4.040^a, 3.420^c, 3.770^d

Space group	a	c	V₀	ρ	E_coh	B₀	B ′ 0
(P6/mmm)	3.641, 3.600^a, 3.6413^b, 3.534^c, 3.508^d, 3.648^e	3.846, 3.840^a, 3.823^b, 3.772^c, 3.745^d, 3.875^e	45.08	0.1774	8.838084	69.17, 63.90^a, 58.90^c, 61.00^d	3.815, 4.000^d, 3.800^c, 3.700^d
(P6₃/mmc)	3.485, 3.558^b, 3.445^c, 3.418^d, 3.552^e	6.228, 6.250^b, 6.148^c, 6.100^d, 6.310^e	67.30	0.1188	6.756029	86.5, 98.0^a, 74.5^c, 78.2^d	3.421, 4.040^a, 3.420^c, 3.770^d

Materials	Space group	a	b	c	V₀	ρ	E_coh	B₀	B ′ 0
Li₂NH	F43m	5.649, 5.077^a			48.02	0.1665	0.7622	93.01	3.581
	Pnma	7.704, 7.733^b	3.75	5.074, 3.60^b, 4.872^b	42.36	0.1888	3.4819534	68.15	3.116
	P6₃/mmc	3.657		5.884	34.11	0.2345	7.6534	211	3.032
	Fm3m	5.045, 5.047^c			32.10	0.2492	6.8820	96.59	3.714
	P-1	4.15, 3.57^d	3.57	6.6045, 3.58^d, 6.426^d	36.42	0.2196	6.7269	78.4	3.441
	Ima2	7.191, 7.118^e	10.071	7.0503, 10.072^e, 7.088^e	44.84?	0.1784	2.27679	91.2	3.160
	pbca	5.12, 5.12^f	10.51	5.267, 10.51^f, 5.27^f	32.79	0.2439	3.3918	59.12	3.947
	Pm3m	3.945			61.40	0.1302	2.4819	112.3	3.017
LiNH₂	I-4	5.0316, 5.032^g, 5.017^h	5.097ⁱ	10.069, 10.256^g, 10363^h, 10.113ⁱ	112.74	0.0709	12.0859	77.92	3.569

Materials	Space group	a	b	c	V₀	ρ	E_coh	B₀	B ′ 0
Li₂NH	F43m	5.649, 5.077^a			48.02	0.1665	0.7622	93.01	3.581
	Pnma	7.704, 7.733^b	3.75	5.074, 3.60^b, 4.872^b	42.36	0.1888	3.4819534	68.15	3.116
	P6₃/mmc	3.657		5.884	34.11	0.2345	7.6534	211	3.032
	Fm3m	5.045, 5.047^c			32.10	0.2492	6.8820	96.59	3.714
	P-1	4.15, 3.57^d	3.57	6.6045, 3.58^d, 6.426^d	36.42	0.2196	6.7269	78.4	3.441
	Ima2	7.191, 7.118^e	10.071	7.0503, 10.072^e, 7.088^e	44.84?	0.1784	2.27679	91.2	3.160
	pbca	5.12, 5.12^f	10.51	5.267, 10.51^f, 5.27^f	32.79	0.2439	3.3918	59.12	3.947
	Pm3m	3.945			61.40	0.1302	2.4819	112.3	3.017
LiNH₂	I-4	5.0316, 5.032^g, 5.017^h	5.097ⁱ	10.069, 10.256^g, 10363^h, 10.113ⁱ	112.74	0.0709	12.0859	77.92	3.569

Space group	P	C₁₁	C₁₂	C₄₄	C₁₃	C₃₃	B	G	E	ν	B/G
P6/mmm	0	177, 165.7^a, 114^b, 122.8^c	28.95, 22.7^a, 38^b, 24.6^c	16.27, 18.1^a, 17.0^b, 16.6^c	10.01, 8.3^a, 4.5^b, 5.4^c	216, 180^a, 118^b, 129.5^c	74.14	63.7	162.08	0.1868	1.163
	17.5	224	32	18.9	11.6	225	86.98	73.89	172.75	0.1899	1.177
P6₃/mmc	20	237	39	46.76	19.01	268	99.54	89.64	206.83	0.1737	1.110
	50	332	51	59	21.6	365	135.26	115.3	269.36	0.1890	1.173