<i>α</i>-FePO<sub>4</sub>高压相变行为的拉曼光谱研究

王越; 徐超文; 李营; 高静

doi:10.11858/gywlxb.20251100

α-FePO₄高压相变行为的拉曼光谱研究

doi: 10.11858/gywlxb.20251100

王越^1,,
徐超文²,
李营²,
高静^1,*, ,

1.
中国科学院深海科学与工程研究所, 海南三亚　572000
2.
中国地震局地震预测研究所, 北京　100036

基金项目: 中国科学院深海科学与工程研究所自主部署项目（E371070101）

详细信息

作者简介:
王　越（1992－），女，硕士，实验师，主要从事极端环境模拟研究. E-mail：wangyue@idsse.ac.cn

通讯作者:
高　静（1988－），女，博士，副研究员，主要从事高压矿物物理研究. E-mail：gaoj@idsse.ac.cn

中图分类号: O521.2; P574.1; P579
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出版历程
- 收稿日期: 2025-05-29
- 修回日期: 2025-06-29
- 网络出版日期: 2025-07-05
- 刊出日期: 2025-10-05

Phase Transition of α-FePO₄ under High Pressure: A Raman Spectroscopy Study

WANG Yue^1
,,
XU Chaowen²,
LI Ying²,
GAO Jing^{1,*
, ,}

1.
Institute of Deep-sea Science and Engineering, Chinese Academy of Sciences, Sanya 572000, Hainan, China
2.
Institute of Earthquake Forecasting, China Earthquake Administration, Beijing 100036, China

摘要

摘要: 鉴于α-FePO₄和α-石英的拓扑同构性，采用金刚石压腔结合拉曼光谱技术，从分子尺度上原位厘定了α-FePO₄在常温高压下的相变行为。在0.2～27.3 GPa压力范围内，揭示了其3个阶段的结构演化特征。在2.8～3.6 GPa区间，α-FePO₄开始发生相变，并于4.6 GPa时完全转变为FePO₄-Ⅱ。在宽泛的4.6～27.3 GPa区间，FePO₄-Ⅱ的结构稳定/亚稳定性依赖于柔性[FeO₆]八面体与刚性[PO₄]四面体的协同形变。在该压力区间，结构无序度增加，振动频率漂移速率减缓，表明结构进入非线性压缩阶段。值得注意的是，在9.8～11.1 GPa临界窗口，P―O键的平均键长和部分振动峰半高宽出现不连续变化，暗示[FeO₆]-[PO₄]网络中存在压力诱导的非均匀应变，推测FePO₄-Ⅱ开始进入亚稳定域。直到卸压至4.6 GPa，FePO₄-Ⅱ的部分结构才恢复有序性，并在常压下保持亚稳态，表现出独特的结构记忆功能。研究结果系统地限定了α-FePO₄的相变压力边界，阐明了正磷酸盐高压结构稳定性的内在调控机制，并预测了其未来结构演化趋势，为解析类石英矿物的高压动态响应提供了重要参考。
- α-石英 /
- 正磷酸盐 /
- 金刚石压腔 /
- 拉曼光谱 /
- 相变
Abstract: Given the topological isomorphism between α-FePO₄ and α-quartz, this study employed a diamond anvil cell coupled with Raman spectroscopy to examine the phase transition of α-FePO₄. The structural evolution across a pressure range of 0.2−27.3 GPa was delineated into three stages. At 2.8−3.6 GPa, α-FePO₄ initiates a phase transition, achieving a complete transformation to FePO₄-Ⅱ at 4.6 GPa. Between 4.6−27.3 GPa, the (meta) stability of FePO₄-Ⅱ is predicated on the cooperative deformation of the adaptable [FeO₆] octahedra and the rigid [PO₄] tetrahedra. The progressive increase in structural disorder and the slowing of vibrational frequency shifts signify a transition to a non-linear compression regime. Notably, in the 9.8−11.1 GPa threshold, discontinuous variations in P―O bond lengths and mode widths serve as evidences of pressure-induced heterogeneous strain within the [FeO₆]-[PO₄] network, suggesting entry into a metastable region. Upon decompression to 4.6 GPa, FePO₄-Ⅱ exhibits partial recovery of structural order, maintaining metastability at ambient conditions, which underscores its unique pressure memory characteristics. This study demarcates the stability boundary of α-FePO₄, elucidates the fundamental mechanisms underpinning stability in orthophosphates, and forecasts structural evolution pathways. The findings offer insights into high-pressure dynamic response of quartz-like minerals.
- α-quartz /
- orthophosphate /
- diamond anvil cell /
- Raman spectroscopy /
- phase transition

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图 1 α-FePO₄在关键压力下(a)和加压过程中(b)的拉曼光谱（光谱右侧的数字代表测谱压力，单位为GPa，字母D代表卸压数据）

Figure 1. Raman spectra of α-FePO₄ at critical pressures (a) and upon compression (b) (The numbers on the right side of the spectra represent the measurement pressure (GPa), and the letter D stands for decompression.)

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图 2 α-FePO₄和FePO₄-Ⅱ的主要振动频率随压力的变化

Figure 2. Principle Raman shifts of α-FePO₄ and FePO₄-Ⅱ at different pressures

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图 3 α-FePO₄和FePO₄-Ⅱ的P―O键的键长随压力的变化

Figure 3. Variations of P―O bond length in α-FePO₄ and FePO₄-Ⅱ as a function of pressure

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图 4 α-FePO₄和FePO₄-Ⅱ的代表性拉曼峰的FWHM随压力的变化关系

Figure 4. FWHM variations of α-FePO₄ and FePO₄-Ⅱ Raman modes at different pressures

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表 1 不同压力下α-FePO₄或FePO₄-Ⅱ的拉曼振动峰峰位和半高宽（100～700 cm⁻¹）

Table 1. Raman shifts and the FWHM of α-FePO₄ or FePO₄-Ⅱ under different pressures (100−700 cm⁻¹)

p/GPa	ν_a(ν_a′)/ cm⁻¹	FWHM(ν_a, ν_a′)/ cm⁻¹	ν_b(ν_b′)/ cm⁻¹	FWHM(ν_b, ν_b′)/ cm⁻¹	ν_c/cm⁻¹	ν_d/cm⁻¹	ν_e/cm⁻¹	ν_f/cm⁻¹	ν_g/cm⁻¹
10⁻⁴	186.70(1)	6.8(1)	284.89(1)	7.4(1)	389.98(1)	415.99(1)	439.61(1)
0.2	187.55(1)	13.1(1)	286.24(1)	11.9(1)		418.87(1)	442.53(1)
0.5	187.90(1)	11.3(1)	287.27(1)	11.0(1)		420.55(1)	444.29(1)
1.2	189.45(1)	9.8(1)	289.33(1)	12.4(1)	397.59(1)	422.21(1)	446.54(1)
2.0	191.25(1)	10.3(1)	290.39(1)	11.5(1)	402.20(1)	425.39(1)	451.92(1)
2.8	192.77(1)	11.6(1)	291.58(1)	12.7(1)	405.51(1)	427.74(1)	455.99(1)
3.6	193.95(1)	12.7(1)	291.93(1)	11.2(1)	406.79(1)	429.17(1)	456.85(1)	516.39(1)	550.13(1)
4.6	194.88(1)	13.4(1)	292.57(1)	12.5(1)				523.21(1)	551.41(1)
5.3	196.21(1)	12.2(1)	293.91(1)	10.9(1)				527.35(1)	551.88(1)
6.2	197.20(1)	11.7(1)	294.49(1)	11.5(1)				529.14(1)	552.78(1)
7.2	198.66(1)	12.9(1)	295.08(1)	12.4(1)				531.08(1)	553.03(1)
8.0	199.80(1)	11.5(1)	295.55(1)	12.8(1)				532.51(1)	553.99(1)
9.2	200.22(1)	12.8(2)	297.00(1)	11.8(1)					554.27(1)
9.8	202.60(1)	13.9(1)	297.89(1)	10.9(1)					555.51(1)
11.1	203.84(1)	10.9(1)	298.46(1)	12.8(1)					555.83(1)
11.9	204.62(1)	13.0(2)	299.56(1)	13.5(1)					556.92(1)
13.0	205.06(1)	12.2(1)	300.12(1)	13.8(1)					557.22(1)
13.8	205.42(1)	15.9(2)	300.45(1)	13.2(1)					558.42(2)
14.5	205.82(1)	13.5(2)	300.85(1)	12.3(1)					558.92(1)
15.4	207.44(1)	16.8(2)	301.31(1)	11.6(1)					559.02(2)
16.7	207.98(1)	18.1(2)	301.88(1)	11.2(1)					560.70(1)
17.2	208.42(1)	15.4(2)	302.53(1)	12.7(1)					561.07(1)
18.2	209.53(1)	18.6(1)	303.45(1)	10.9(1)					561.52(3)
19.2	210.02(1)	16.3(2)	303.62(1)	11.5(1)					561.77(1)
20.5	210.08(1)	18.9(2)	303.98(1)	12.8(1)					562.12(3)
22.0	211.62(1)	20.6(3)	304.63(1)	13.2(1)					563.32(2)
23.5	212.45(1)	19.3(2)	304.93(1)	12.5(1)					564.38(2)
24.0	213.19(1)	21.0(2)	305.06(1)	12.8(1)					565.32(2)
25.8	213.82(1)	19.3(2)	305.62(1)	11.2(1)					564.99(1)
26.4	214.31(1)	20.5(3)	306.24(1)	13.9(1)					565.92(1)
27.3	214.72(1)	18.8(3)	306.62(1)	11.7(1)					566.85(3)

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表 2 不同压力下α-FePO₄或FePO₄-Ⅱ的拉曼振动峰峰位和半高宽（900～1200 cm⁻¹）

Table 2. Raman shifts and the FWHM of α-FePO₄ or FePO₄-Ⅱ under different pressures (900−1200 cm⁻¹)

p/GPa	ν_h/cm⁻¹	FWHM(ν_h)/ cm⁻¹	ν_i/cm⁻¹	FWHM(ν_i)/ cm⁻¹	ν_j/cm⁻¹	FWHM(ν_j)/ cm⁻¹	ν_k(ν_k′)/cm⁻¹	FWHM(ν_k, ν_k′)/ cm⁻¹
10⁻⁴			1012.82(1)	4.3(1)	1053.04(1)	8.3(1)	1168.20(1)	11.3(1)
0.2			1014.46(1)	9.8(1)
0.5			1015.14(1)	9.4(1)
1.2			1017.35(1)	9.5(1)
2.0			1019.84(1)	10.4(1)
2.8			1020.12(1)	10.7(1)
3.6	967.78(1)	20.7(1)	1023.69(1)	21.7(1)	1058.21(1)	13.4(1)	1161.24(1)	19.3(1)
4.6	970.73(1)	24.7(1)			1059.75(1)	15.6(1)	1164.04(1)	18.5(1)
5.3	974.53(1)	22.8(1)			1061.09(1)	18.4(1)	1168.42(1)	17.5(1)
6.2	977.97(1)	21.9(1)			1061.64(1)	19.3(1)	1169.47(1)	19.2(1)
7.2	981.90(1)	25.9(1)			1063.75(1)	15.2(1)	1173.29(1)	19.7(1)
8.0	983.70(1)	27.4(1)			1064.13(1)	13.4(1)	1173.49(1)	16.2(1)
9.2	987.32(1)	29.6(1)			1065.34(1)	18.5(1)	1176.32(1)	17.4(1)
9.8	989.82(1)	31.0(1)			1066.05(1)	17.5(1)	1178.51(1)	16.6(1)
11.1	991.95(1)	29.0(1)			1068.99(1)	19.2(1)	1179.35(1)	18.5(1)
11.9	996.82(1)	30.6(1)			1069.51(1)	14.9(1)	1180.20(1)	16.7(1)
13.0	1000.92(1)	29.0(1)			1070.21(1)	20.4(1)	1182.01(1)	19.3(1)
13.8	1001.12(1)	30.2(1)			1071.31(1)	15.2(1)	1184.32(1)	18.3(1)
14.5	1003.45(1)	29.4(1)			1071.62(1)	16.7(1)	1185.85(1)	15.6(1)
15.4	1004.62(1)	29.8(1)			1071.89(1)	18.9(1)	1186.44(1)	17.3(1)
16.7	1008.22(1)	29.7(1)			1072.57(1)	19.3(1)	1187.02(1)	19.0(1)
17.2	1009.41(1)	29.0(1)			1072.65(1)	14.9(1)	1189.54(1)	16.9(1)
18.2	1011.42(1)	30.1(1)			1073.86(1)	16.8(1)	1190.96(1)	17.4(1)
19.2	1012.94(1)	28.6(1)			1074.09(1)	15.0(1)	1192.02(1)	15.3(1)
20.5	1017.18(1)	29.3(1)			1074.91(1)	19.0(1)	1193.11(1)	18.3(1)
22.0	1020.42(1)	28.6(1)			1076.29(1)	18.6(1)	1194.82(1)	17.4(1)
23.5	1021.52(1)	25.7(1)			1077.02(1)	17.4(1)	1195.21(1)	16.9(1)
24.0	1023.31(1)	24.8(1)			1077.73(1)	14.2(1)	1196.74(1)	19.7(1)
25.8	1026.42(1)	27.9(1)			1078.21(1)	16.9(1)	1197.12(1)	17.4(1)
26.4	1028.52(1)	26.8(1)			1078.89(1)	15.2(1)	1197.94(1)	16.4(1)
27.3	1029.68(1)	27.6(1)			1079.08(1)	15.9(1)	1198.22(1)	13.4(1)

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