NiCl2晶体生长的数值模拟

doi:10.7503/cjcu20150352

摘要/Abstract

摘要：

利用剑桥总能量连续软件包(CASTEP)程序, 采用密度泛函理论(DFT)对NiCl₂晶体(003), (101), (104), (018)和(113)面真空slab模型进行了总能量、表面能以及能带结构和态密度的计算, 采用布拉维法则和唐纳-哈克定律(BFDH)形貌预测方法对氯化镍晶体形貌及其各晶面生长习性进行了计算. 收敛性测试结果表明真空层厚度为0.6 nm及模型厚度为3层原子对表面能计算影响较小. DFT计算结果显示, 当氯化镍晶体以(003)面为主要显露面时, 能量状态较为稳定, 而以(101), (104), (018)和(113)面显露较多时, 则能量稳定性较差. (003)面的前线价电子较为活跃, 其晶面可能存在与溶液中离子、分子或是晶体生长基元发生键合的“活性点”, 能隙较大说明该面内层电子较为稳定. 能带结构和态密度图分析显示(003)面费米能级附近能量较高的能带数量少于其它晶面, 再次证明其为主要显露面时体系热力学性质较为稳定. BFDH对氯化镍晶体形貌的计算成功预测了显露面族(003)和(101), 并且(003)面是最重要晶面. 计算结果表明, 氯化镍晶胞和各表面真空slab模型的生长习性存在差异, 氯化镍晶胞、 (003)、 (101)和(113)面slab模型均趋向于生长为六棱柱或六角板状晶体, (104)和(018)面slab模型则趋向于生长为棒状晶体.

关键词: 氯化镍, 表面能, 密度泛函理论, 晶体形貌

Abstract:

Based on the density function theory(DFT) calculation of crystal faces (003), (101), (104), (018) and (113) of NiCl₂ via CASTEP program, total energy, surface energy, band structures and density of states(DOS) were investigated. The crystal morphology of NiCl₂ and the growth habit of the surface of NiCl₂ were calculated by Bravais-Friedel Donnay-Harker(BFDH) rules. The results show that vacuum width of 0.6 nm and atom layer of 3 are reasonable to the surface energy calcution. The energy state of NiCl₂ is far more stable when face (003) is mainly unfold faces, while the energy state would be instable when faces (101), (104), (018) and (113) are the mainly unfolded. The electric structure results show that the front valence electron of face (003) is active correspondingly. That is there may be some activity points on this face. The larger energy band gap of it shows that the inner electrons are more stable. The band structures and DOS analysis show that the number of high energy band of (003) slab near the Fermi energy is less than that of other slabs, which proves the system is more stable no thermodynamics when (003) is mainly unfold.BFDH calculation on NiCl₂ predicts the unfold faces (003) and (101) successfully and indicates (003) is the most important face. Other results show that the growth habits of NiCl₂ cell and its surface slabs are different, NiCl₂ cell, (003), (101) and (113) slabs are inclined to form crystal with hexagonal plate and bulk shapes, (104) and (018) slabs are inclined to form crystal with rod shape.

Key words: Nickel chloride, Surface energy, Density functional theory, Crystal morphology

中图分类号:

O641

TrendMD:

肖志夏, 朱艳丽, 赵勇, 邢家超, 焦清介. NiCl₂晶体生长的数值模拟. 高等学校化学学报, 2015, 36(12): 2497.

XIAO Zhixia, ZHU Yanli, ZHAO Yong, XING Jiachao, JIAO Qingjie. Simulation on the Growth of NiCl₂ Crystal^†. Chem. J. Chinese Universities, 2015, 36(12): 2497.

图/表 11

Fig.1 Standard powder diffraction pattern(a) and powder diffraction pattern simulated by Reflex code(b) of NiCl2

Fig.2 Structure of NiCl2 cell

Fig.3 Surface slab models of NiCl2 Vacuum along the edge of the side. (A) (003); (B)(101); (C) (104); (D)(018); (E) (113).

Fig.4 Surface energies with increasing vacuum width(A) and slab thickness(B)

Fig.5 Total energy and surface energy of all surface slab models calculated at LDA-CA-PZ basis set

Fig.6 Fermi energy of NiCl2 surface slab models

Fig.7 Density of states(DOS) of NiCl2 surface slab models (A) (003); (B) (101); (C) (104); (D) (018); (E) (113).

Fig.8 Crystal growth habit of NiCl2 calculated by BFDH method

Fig.9 Growth habit of the facet slabs of NiCl2 calculated by BFDH method (A) (003); (B) (101); (C) (104); (D) (018); (E) (113).

Table 1 Unique number of facets and its percents of total facet area of slab models calculated by BFDH method

(003)		(101)		(104)		(018)		(113)
(hkl)	δ(%)	(hkl)	δ(%)	(hkl)	δ(%)	(hkl)	δ(%)	(hkl)	δ(%)
(001)	40.1	(001)	33.7	(001)	31.4	(001)	26.8	(001)	27.8
(00 $1 ˉ$ )	40.1	(00 $1 ˉ$ )	33.7	(00 $1 ˉ$ )	31.4	(00 $1 ˉ$ )	26.8	(00 $1 ˉ$ )	27.8
(100)	3.3	(100)	9.7	(100)	12.4	(010)	17.1	(010)	9.9
( $1 ˉ$ 00)	3.3	( $1 ˉ$ 00)	9.7	( $1 ˉ$ 00)	12.4	(0 $1 ˉ$ 0)	17.1	(0 $1 ˉ$ 0)	9.9
(010)	3.3	(1 $1 ˉ$ 0)	3.3	(010)	6.2	(100)	6.1	(100)	9.8
(0 $1 ˉ$ 0)	3.3	(010)	3.3	(0 $1 ˉ$ 0)	6.2	( $1 ˉ$ 00)	6.1	( $1 ˉ$ 00)	9.8
(110)	3.3	( $1 ˉ$ 10)	3.3					( $1 ˉ$ 10)	2.5
( $1 ˉ$ $1 ˉ$ 0)	3.3	(0 $1 ˉ$ 0)	3.3					(1 $1 ˉ$ 0)	2.5

Table 1 Unique number of facets and its percents of total facet area of slab models calculated by BFDH method

(003)		(101)		(104)		(018)		(113)
(hkl)	δ(%)	(hkl)	δ(%)	(hkl)	δ(%)	(hkl)	δ(%)	(hkl)	δ(%)
(001)	40.1	(001)	33.7	(001)	31.4	(001)	26.8	(001)	27.8
(00 $1 ˉ$ )	40.1	(00 $1 ˉ$ )	33.7	(00 $1 ˉ$ )	31.4	(00 $1 ˉ$ )	26.8	(00 $1 ˉ$ )	27.8
(100)	3.3	(100)	9.7	(100)	12.4	(010)	17.1	(010)	9.9
( $1 ˉ$ 00)	3.3	( $1 ˉ$ 00)	9.7	( $1 ˉ$ 00)	12.4	(0 $1 ˉ$ 0)	17.1	(0 $1 ˉ$ 0)	9.9
(010)	3.3	(1 $1 ˉ$ 0)	3.3	(010)	6.2	(100)	6.1	(100)	9.8
(0 $1 ˉ$ 0)	3.3	(010)	3.3	(0 $1 ˉ$ 0)	6.2	( $1 ˉ$ 00)	6.1	( $1 ˉ$ 00)	9.8
(110)	3.3	( $1 ˉ$ 10)	3.3					( $1 ˉ$ 10)	2.5
( $1 ˉ$ $1 ˉ$ 0)	3.3	(0 $1 ˉ$ 0)	3.3					(1 $1 ˉ$ 0)	2.5

Table 2 Relative surface/volume ratio and volume slab models calculated by BFDH method

(003)		(101)		(104)		(018)		(113)
(S/V)/nm^-1	V/nm³	(S/V)/nm^-1	V/nm³	(S/V)/nm^-1	V/nm³	(S/V)/nm^-1	V/nm³	(S/V)/nm^-1	V/nm³
1.983	34.13	1.572	23.39	1.541	20.33	1.471	16.45	1.335	16.80

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NiCl₂晶体生长的数值模拟

Simulation on the Growth of NiCl₂ Crystal^†

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