Rb2MGe3S8 (M=Zn, Cd): [MGe3S8]2–单元构型变换导致化合物从中心到非心的转变※

doi:10.6023/A22010020

化学学报 ›› 2022, Vol. 80 ›› Issue (5): 633-639.DOI: 10.6023/A22010020 上一篇下一篇

所属专题：中国科学院青年创新促进会合辑

研究论文

Rb₂MGe₃S₈ (M=Zn, Cd): [MGe₃S₈]^2–单元构型变换导致化合物从中心到非心的转变^※

柴贤丹^a^,^b, 陈文发^b, 闫秋楠^b, 刘彬文^b, 姜小明^b^,^*(), 郭国聪^b^,^*()

a 福建师范大学化学与材料学院福州 350007
b 中国科学院福建物质结构研究所结构化学国家重点实验室福州 350608

投稿日期:2022-01-12 发布日期:2022-02-17
通讯作者: 姜小明, 郭国聪
作者简介:
^※庆祝中国科学院青年创新促进会十年华诞.
基金资助:
国家自然科学基金(22075283); 国家自然科学基金(22175172); 国家自然科学基金(92161125); 中国科学院青年创新促进会(2020303); 中国科学院青年创新促进会(2021300)

Rb₂MGe₃S₈ (M=Zn, Cd): Non-Centrosymmetry Transformation Led by Structure Change of [MGe₃S₈]^2- Unit^※

Xiandan Chai^a^,^b, Wenfa Chen^b, Qiunan Yan^b, Binwen Liu^b, Xiaoming Jiang^b(), Guocong Guo^b()

a School of Chemistry and Materials, Fujian Normal University, Fuzhou, 350007
b State Key Laboratory of Structural Chemistry, Fujian Institute ofResearch on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350608

Received:2022-01-12 Published:2022-02-17
Contact: Xiaoming Jiang, Guocong Guo
About author:
^※Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Natural Science Foundation of China(22075283); National Natural Science Foundation of China(22175172); National Natural Science Foundation of China(92161125); Youth Innovation Promotion Association of Chinese Academy of Sciences(2020303); Youth Innovation Promotion Association of Chinese Academy of Sciences(2021300)

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1. Supporting Information-A21120618.pdf(1031KB)

摘要/Abstract

在本工作中, 利用高温固相法成功合成了两个碱金属硫属化合物Rb₂MGe₃S₈ [M=Zn (1), Cd (2)]. 化合物1, 2都为二维层状结构且均具备大的光学带隙, 化合物1和2的实验带隙分别为3.24和3.16 eV. 化合物1属于P-1中心对称群, 化合物2属于非心P2(1)2(1)2(1)空间群且具有一定的非线性光学(NLO)效应, 在粒径为50~75 μm时与KH₂PO₄ (KDP)相当(@1064 nm). 化合物2的激光损伤阈值为AgGaS₂的16.6倍. 化合物1, 2的分子式化学计量比相同但展示不同的对称性, 通过分析它们的晶体结构发现, 其基本构造单元[MGe₃S₈]^2–在两化合物中构型的不同导致化合物1、2对称性发生中心到非心的转变. 为了深入了解化合物2的NLO效应的起源, 基于密度泛函理论对其进行了电子能带结构和NLO极化率的理论计算.

关键词: 硫属化合物, 非线性光学, 中心到非心转变, 理论计算

Infrared nonlinear (IR NLO) optical crystals have an essential position in military and civilian fields because of their ability to convert lasers from near infrared (NIR) to mid/far infrared (MIR/FIR). In this work, two alkali-metal chalcogenides, Rb₂MGe₃S₈[M=Zn (1), Cd (2)], were successfully synthesized by high-temperature solid-state reactions. Both compounds feature a two-dimensional layered structure and have a large optical band-gap, the experimental band-gap of 1 and 2 are 3.24 eV and 3.16 eV, respectively. Compound 1 belongs to the centrosymmetric group P-1, while 2 belongs to the non-centrosymmetric space group P2(1)2(1)2(1) and exhibits obvious NLO effect, which is comparable to that of KH₂PO₄ (KDP) (@1064 nm) at the particle size of 50~75 μm. Particle-size dependent NLO response measurements indicated that 2 is non-phase-matchable. Compound 2 exhibits a high laser-induced damage threshold of 16.6×AGS at 1064 nm. Through the analysis of the crystal structures of these two compounds, the reason why their formulas have the same stoichiometric ratio but symmetries are different is the structure change of basic building unit [MGe₃S₈]^2– in 1 and 2. All M atoms in both compounds are coordinated by four S atoms to form MS₄ tetrahedra. In each [CdGe₃S₈]^2–unit of 2, three S atoms bonded to the Cd atom are also bonded to all Ge atoms in that unit, that is to say, each CdS₄ tetrahedron is connected to the other three GeS₄ tetrahedra by sharing S vertices. Unlike the coordination manner in the [CdGe₃S₈]^2– unit of 2, there are only two S atoms bonded to both Zn and Ge atoms in [ZnGe₃S₈]^2–unit of 1. This structure change of [MGe₃S₈]^2– unit eventually led to the non-centrosymmetric transformation. What’s more, to get insight into the origin of NLO effect of 2, theoretical calculations of electronic band structure and NLO susceptibility were performed based on density functional theory.

Key words: chalcogenides, nonlinear optical, non-centrosymmetric transformation, theoretical calculation

引用此文

柴贤丹, 陈文发, 闫秋楠, 刘彬文, 姜小明, 郭国聪. Rb₂MGe₃S₈ (M=Zn, Cd): [MGe₃S₈]^2–单元构型变换导致化合物从中心到非心的转变^※[J]. 化学学报, 2022, 80(5): 633-639.

Xiandan Chai, Wenfa Chen, Qiunan Yan, Binwen Liu, Xiaoming Jiang, Guocong Guo. Rb₂MGe₃S₈ (M=Zn, Cd): Non-Centrosymmetry Transformation Led by Structure Change of [MGe₃S₈]^2- Unit^※[J]. Acta Chimica Sinica, 2022, 80(5): 633-639.

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图/表 8

图 1. 化合物1 (a)与2 (b)的模拟与实验XRD粉末衍射图(这两个化合物模拟的XRD谱上有些峰的强度与实测的不一致, 主要是由于它们样品中存在织构, 这种情况经常出现在一些层状晶体结构的化合物中)

Figure 1. Simulated and experimental powder XRD patterns of 1 (a) and 2 (b) (the intensities of some peaks on the experimental patterns are significantly different from those on the simulated patterns due to the preferred orientation of the sample, which usually exists in compounds with layered structures)

Empirical formula	Rb₂ZnGe₃S₈
F_w	1369.31
Temperature/K	293(2)
Space group	P-1
a/nm	0.71792(4)
b/nm	0.74790(4)
c/nm	1.44305(7)
α/(°)	88.774(4)
β/(°)	84.409(4)
γ/(°)	72.211(5)
Volume/nm³	0.73424(7)
Z	2
D_calc/(g•cm^–3)	3.214
μ/mm^–1	15.378
GOF on F²	1.037
R₁^a [I≥2σ(I)]	0.0450
wR₂^b [I≥2σ(I)]	0.1142
R₁^a [all data]	0.0649
wR₂^b [all data]	0.1230
(Δρ_max/Δρ_min)/(e•nm^–3)	1080/–1160

表1. 化合物1的晶体数据和结构精修参数

Table 1. Crystal data and structure refinement parameters of 1

Empirical formula	Rb₂CdGe₃S₈
F_w	1515.18
Temperature/K	293(2)
Space group	P2(1)2(1)2(1)
a/nm	0.73459(2)
b/nm	1.22234(4)
c/nm	1.69163(7)
α/(°)	90
β/(°)	90
γ/(°)	90
Volume/nm³	1.51895(9)
Z	2
D_calc/(g•cm^–3)	3.313
μ/mm^–1	14.688
GOF on F²	1.002
R₁^a [I≥2σ(I)]	0.0310
wR₂^b [I≥2σ(I)]	0.0644
R₁^a [all data]	0.0400
wR₂^b [all data]	0.0671
Flack	0.988(14)
(Δρ_max/Δρ_min)/(e•nm^–3)	790/–960

表 2. 化合物2的晶体数据和结构精修参数

Table 2. Crystal data and structure refinement parameters of 2

图2. 化合物1 (a)和2 (b)的红外光谱图, 化合物1 (c)和2 (d)的紫外漫反射谱转换后的吸收光谱图

Figure 2. IR spectra of 1 (a) and 2 (b), absorption spectra of 1 (c) and 2 (d) converted from diffuse reflectance spectra

图3. (a)在1.064 μm激光照射下, 粒径为50~75 μm的化合物2与KDP的SHG响应; (b)化合物2与参比样品KDP随粒径变化的SHG响应

Figure 3. (a) SHG intensities of 2 and KDP at the particle size of 50~75 μm at incident wavelength of 1.06 μm laser; (b) particle size dependence of SHG intensities of 2 and the reference KDP

图4. (a)化合物1中沿a方向的二维[ZnGe3S8]2–层; (b)化合物1中沿b方向的 [ZnGe3S8]2–层; (c)化合物1中的一个[ZnGe3S8]2–单元; (d)化合物2沿c方向的二维[Cd2Ge3S8]2-层; (e)化合物2中沿b方向的[Cd2Ge3S8]2-层; (f)化合物2中的一个[CdGe3S8]2–单元

Figure 4. (a) A [ZnGe3S8]2– layer of 1 viewed down the a-direction. (b) A [ZnGe3S8]2– layer of 1 viewed down the b-direction. (c) A [ZnGe3S8]2– unit in 1. (d) A [CdGe3S8]2– layer of 2 viewed down the c-direction. (e) A [CdGe3S8]2– layer of 2 viewed down the b-direction. (f) A [CdGe3S8]2– unit in 2

图5. 通过计算得到的化合物2的SHG系数张量d14 (a)、有效SHG系数deff (b)、与能量相关的双折射率(c)和相位匹配曲线(d)

Figure 5. Calculated SHG coefficient tensors d14 (a), effective SHG coefficient deff (b), the energy-dependent birefringence (c) and phase-matching curves (d) of 2

图6. 化合物1 (a)和化合物2 (b)的电子能带图; 化合物1 (c)和化合物2 (d)的部分态密度与总态密度图

Figure 6. Electronic band structure of 1 (a) and 2 (b); total and partial density of states of 1 (c) and 2 (d)

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Rb₂MGe₃S₈ (M=Zn, Cd): [MGe₃S₈]^2–单元构型变换导致化合物从中心到非心的转变^※

Rb₂MGe₃S₈ (M=Zn, Cd): Non-Centrosymmetry Transformation Led by Structure Change of [MGe₃S₈]^2- Unit^※

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