高氯酸钠高压相变的拉曼光谱证据

何运鸿; 田雨; 赵慧芳; 姜峰; 谭大勇; 肖万生

doi:10.11858/gywlxb.20180543

高氯酸钠高压相变的拉曼光谱证据

doi: 10.11858/gywlxb.20180543

何运鸿^{1, 2, 3,},
田雨^{1, 2, 3},
赵慧芳^{1, 2, 3},
姜峰^{1, 2, 3},
谭大勇^{1, 2},
肖万生^{1, 2,*, ,}

1.
中国科学院广州地球化学研究所矿物学与成矿学重点实验室, 广东广州 510640
2.
广东省矿物物理与材料研究开发重点实验室, 广东广州 510640
3.
中国科学院大学, 北京 100049

基金项目:

国家自然科学基金 41572030

中国科学院战略性先导科技专项（B类） XDB18010403

详细信息

作者简介:
何运鸿(1992-), 女, 硕士研究生, 主要从事高压矿物学研究.E-mail:heyunhong@gig.ac.cn

通讯作者:
肖万生(1968-), 男, 博士, 研究员, 主要从事高压矿物物理研究.E-mail:wsxiao@gig.ac.cn

中图分类号: O521.2;P311.9
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出版历程
- 收稿日期: 2018-04-23
- 修回日期: 2018-06-11

Raman Evidences for Phase Transition of Sodium Perchlorate at High Pressure

HE Yunhong^{1, 2, 3
,},
TIAN Yu^{1, 2, 3},
ZHAO Huifang^{1, 2, 3},
JIANG Feng^{1, 2, 3},
TAN Dayong^{1, 2},
XIAO Wansheng^{1, 2,*
, ,}

1.
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
2.
Key Lab of Guangdong Province for Mineral Physics and Materials, Guangzhou 510640, China
3.
University of Chinese Academy of Sciences, Beijing 100049, China

摘要

摘要: 利用金刚石压腔高压装置，在0~20 GPa压力范围对高氯酸钠（NaClO₄）开展室温高压原位拉曼光谱测试，结合密度函数理论，计算NaClO₄几种可能结构的拉曼光谱，研究NaClO₄的压致相变现象，并确定其高压相晶体结构。实验结果显示：常温下硬石膏型结构的NaClO₄在约4 GPa时开始相变，在低压相ClO₄^-四面体内模振动ν₁（A_g）拉曼峰的低波数侧出现新峰，并在ν₂、ν₃、ν₄波数区出现多个新峰，反映高压相仍保持ClO₄^-四面体配位特征；如同NaClO₄低压相，高压相也未观察到离子间的晶格振动峰；相变在6.1 GPa时转变完全，直到最高实验压力19.5 GPa，也没有观察到进一步的相变现象。卸压过程中，于3.1 GPa开始从高压相转变成低压硬石膏相，1.7 GPa时相变完成。对比8.8 GPa实验观察的NaClO₄高压相拉曼光谱和理论计算的8.0 GPa时3种可能高压相（AgMnO₄型、重晶石型和独居石型）的拉曼光谱发现，实验观测结果与计算的独居石型结构基本一致，而与AgMnO₄型结构和重晶石型结构有明显差别。由此确定实验观察的NaClO₄高压相为独居石型结构，与相同结构的典型矿物硬石膏（CaSO₄）于2 GPa转变成独居石结构相一致。上述实验现象表明，NaClO₄在4 GPa左右发生可逆的重构型相变，与文献报道的NaClO₄于2 GPa左右转变成AgMnO₄型结构、于3 GPa左右进一步转变成重晶石型结构不一致，推测可能与他们的样品中含有少量水有关，或与高温高压实验环境有关，高压同时高温也许导致NaClO₄更复杂的变化。研究结果对于理解火星上广泛存在的高氯酸盐是否与火星内部火山作用相关，以及地球内部氯元素在板块俯冲、地幔柱等物质循环过程中的可能变化和作用有所助益。
- 高氯酸钠 /
- 高压 /
- 拉曼光谱 /
- 结构相变 /
- 独居石型结构
Abstract: Using a diamond anvil cell apparatus, we investigated the sodium perchlorate (NaClO₄) by Raman spectroscopy at pressure up to 20 GPa, and calculated the Raman spectra of anhydrite-(Cmcm), monazite-(P2₁/n), AgMnO₄-(P2₁/n), and barite-type (Pnma) structures of NaClO₄ by density function theory.The experimental data show that anhydrite-type NaClO₄ undergoes a structural transition at about 4 GPa.A new peak at lower Raman frequencies (975 cm^-1) than that of the ClO₄^- internal mode ν₁ (A_g) of the NaClO₄ ambient phase was obviously observed at 4.4 GPa.At the same time, several peaks at the corresponding wave numbers of the ClO₄^- internal modes (ν₂、ν₃、ν₄) arise.The phase transition is completed at about 6.1 GPa, and remains stable up to 19.5 GPa.The high pressure structure can be recovered at about 3.1 GPa in decompression.By comparison with the calculated Raman spectral profiles (at 8.0 GPa) of three potential high pressure structures, we infer that the high pressure phase has a monoclinic monazite-type structure.The pressure-induced phase transition of NaClO₄ is consistent with the anhydrite-monazite phase transition found in CaSO₄ at about 2 GPa.However, our finding appears inconsistency with the previous observations that the anhydrite-type NaClO₄ transforms to AgMnO₄-type at about 2 GPa and furthermore to the barite-type structure at around 3 GPa.The previous results could probably be influenced by the moisture of the sample combining with the high temperature and high pressure conditions.It may bring more complicated changes by simultaneous high pressure and high temperature environments.The research progress contributes to the understanding of not only the relationship between volcanic activity and the widespread distribution of perchlorate on Mars, but also the changes and functions of chlorine element during the recycles of subduction and mantle plume in the Earth's deep interior.
- NaClO₄ /
- high pressure /
- Raman spectrum /
- phase transition /
- Monazite-type structure

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图 1 NaClO₄和NaClO₄·H₂O常压拉曼光谱(星号标记的885和960cm^-1峰为ClO₄^-四面体内模ν₂振动的倍频峰)

Figure 1. Raman spectra of anhydrite-type NaClO₄ and NaClO₄·H₂O at ambient conditions (Asterisks indicate overtones of the ClO₄^- tetrahedra internal modes of ν₂ located at 885 and 960cm^-1)

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图 2 加压和卸压过程中NaClO₄的代表性拉曼光谱(图 2(a)显示加压过程，其中4.1GPa曲线指示NaClO₄开始相变；图 2(b)表示卸压过程，3.5GPa曲线表示相变开始。箭头及对应数字指示相变过程中出现的新峰。Ⅰ和Ⅱ分别代表硬石膏相和独居石相，Ⅰ+Ⅱ和(Ⅰ+Ⅱ)分别代表加压和卸压过程中两相共存。ν₂、ν₃和ν₄振动区间纵坐标放大1倍)

Figure 2. Several representative Raman spectra of NaClO₄ observed at various pressures (The Fig. 2(a) shows Raman spectra collected in the compressing process, in which the 4.1GPa profile indicates the beginning of phase transition.The Fig. 2(b) displays Raman spectra observed in the decompressing process, in which the 3.5GPa spectrum manifests the phase transition occurring.The arrows and its corresponding numbers denote the emerging new peaks. Ⅰ, Ⅱ, Ⅰ+Ⅱ, and (Ⅰ+Ⅱ) correspond to anhydrite-type, monazite-type and two-phase coexistence of NaClO₄ in compression and decompression, respectively.In the graphics, the vertical axis of the ν₂, ν₃ and ν₄ sections are doubled.)

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图 3 NaClO₄拉曼频率随压力的变化关系(Ⅰ和Ⅱ分别代表硬石膏相和独居石相，Ⅰ+Ⅱ和(Ⅰ+Ⅱ)分别代表加压和卸压过程中两相共存；三角形和圆形分别表示硬石膏相和独居石相，实心和空心分别代表加压过程和卸压过程)

Figure 3. Pressure dependence of Raman vibrational modes of NaClO₄ (The Roman letters of Ⅰ, Ⅱ, Ⅰ+Ⅱ, (Ⅰ+Ⅱ) correspond to anhydrite-type, monazite-type and two-phase coexistence of NaClO₄ on compression and decompression, respectively.The triangles and cycles denote the anhydrite-type and monazite type NaClO₄, of which solid and open symbols indicate the compressing and decompressing process, respectively.)

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图 4 含少量水的NaClO₄在加压过程中的代表性拉曼光谱(2.0GPa曲线表示开始相变，4.2GPa曲线表示两相共存。图中ν₂、ν₃、ν₄的振动区间纵坐标放大1倍)

Figure 4. Representative Raman spectra of NaClO₄ with minor water at various pressures observed in compression process (The 2.0GPa spectrum suggests the beginning of phase transition, indicated by the new Raman frequency bands.The 4.2GPa spectrum reflects coexistence of the high-pressure phase and low-pressure phase of NaClO₄. The vertical axis of the ν₂, ν₃, ν₄ sections are doubled.)

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图 5 实验观察和理论计算的NaClO₄拉曼光谱(曲线a和曲线c分别为常压和8.8GPa时实验观测的拉曼光谱，曲线b为理论计算的1.5GPa时NaClO₄硬石膏相的拉曼光谱，曲线d、e、f分别为理论计算的8.0GPa时独居石相﹑重晶石相和AgMnO₄相NaClO₄的拉曼光谱)

Figure 5. Calculated Raman spectra of anhydrite-type, monazite-type, barite-type, and AgMnO₄-type NaClO₄ and experimental spectra (Experimental spectra collected at 0.1MPa and 8.8GPa are shown as a and c curves.The b spectrum is the calculated Raman spectrum at 1.5GPa with anhydrite-type structure.The d, e, f curves are the calculated Raman spectra at 8.0 GPa with monazite-type, barite-type, and AgMnO₄-type structure, respectively.)

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表 1 群论预测NaClO₄硬石膏相、独居石相、AgMnO₄相和重晶石相的拉曼振动模

Table 1. Group theory prediction of Raman modes of anhydrite-type, monazite-type, AgMnO₄-type, and barite-type NaClO₄

Internal vibrationalmodes	Symmetry classification
Internal vibrationalmodes	Anhydrite-type	Monazite-type	AgMnO₄-type	Barite-type
ν₁	A_g	A_g+B_g	A_g+B_g	A_g+B_2g
ν₂	A_g+B_2g	2A_g+2B_g	2A_g+2B_g	A_g+B_1g+ B_2g+B_3g
ν₃	A_g+B_1g+B_3g	3A_g+3B_g	3A_g+3B_g	2A_g+B_1g+ 2B_2g+ B_3g
ν₄	A_g+B_1g+B_3g	3A_g+3B_g	3A_g+3B_g	2A_g+B_1g+ 2B_2g+ B_3g
Total	6A_g+5B_1g+2B_2g+5B_3g	18A_g+ 18B_g	18A_g+ 18B_g	11A_g+7B_1g+11B_2g+7B_3g

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表 2 实验观察(0.1MPa)及理论计算(1.5GPa)的硬石膏型NaClO₄拉曼频率及其归属

Table 2. Raman modes assignment and frequencies of anhydrite-type NaClO₄ observed at 0.1MPa and calculated at 1.5GPa

Internal vibrational modes	Symmetry classification	Raman frequency/cm^-1
Internal vibrational modes	Symmetry classification	Exp.	Calc.	Ref.[30]	Ref.[31]
ν₂	B_2g	444	424	444	444
ν₂	A_g	481	466	484	483
ν₄	B_1g	620	593	620	629
	B_3g	628	600	6296	620
	A_g	655	635	654	629
ν₁	A_g	952	932	953	953
ν₃	B_1g	1089	1069	1088	1148
	A_g	1098	1085	1097	1145
	B_3g	1146	1132	1148	1087

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表 3 NaClO₄硬石膏相和独居石相的拉曼频率随压力的变化

Table 3. Pressure coefficients of observed Raman bands for anhydrite-type and monazite-type NaClO₄

Anhydrite-type				Monazite-type
Internal vibrationalmodes	Symmetryclassification	ω/cm^-1 (p=3.0GPa)	(dω/dp)/ (cm^-1·GPa^-1)	Internal vibrationalmodes	Symmetryclassification	ω/cm^-1(p=7.0GPa)	(dω/dp)/(cm^-1·GPa^-1)
ν₂	B_2g	446	0.5(2)	ν₂	B_g	465	2.2(1)
ν₂	A_g	496	4.1(2)		A_g	480	2.4(0)
ν₄	B_1g	625	1.5(1)		A_g	497	2.4(1)
	B_3g	635	2.0(2)		B_g	510	2.6(1)
	A_g	668	3.3(4)	ν₄	A_g	619	0.8(1)
ν₁	A_g	974	6.8(3)		B_g	631	1.4(1)
ν₃	B_1g	1102	3.9(1)		A_g	643	1.8(1)
	A_g	1116	5.3(1)		B_g	659	2.3(1)
	B_3g	1174	7.8(7)		A_g	667	1.8(1)
				ν₁	A_g	986	4.7(1)
				ν₃	A_g	1113	3.9(1)
					A_g	1132	4.1(1)
					A_g	1148	4.3(1)
					B_g	1160	3.9(1)
					B_g	1172	5.0(1)
					B_g	1208	5.3(2)
Note:Numbers in parentheses indicate standard deviation.

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