Micro-FTIR Analysis and First-Principle Calculation of Structural Water in Coesite from NAMs
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摘要: 从微观尺度研究结构水的分布状态可以为超高压变质岩的形成环境、构造演化动力学过程提供重要的依据.为探讨大别山地区超高压变质岩中"名义上无水矿物"（nominal anhydrous minerals，NAMs）结构水的分布特征、赋存状态与超微结构缺陷的关系，对大别山石马地区榴辉岩中的柯石英进行了傅立叶变换红外光谱（FTIR）分析和第一性原理计算.FTIR研究表明柯石英主要吸收峰为（Ⅰ）3 561~3 580 cm-1、（Ⅱ）3 433~3 462 cm-1和（Ⅲ）3 412~3 425 cm-1；柯石英颗粒结构水含量为15×10-6~52×10-6，平均值是32×10-6.第一性原理理论计算得到了柯石英（4H）Si和（AlH）Si复合缺陷超晶胞模型（2×1×1）的形成能分别是-4.92 eV和-3.10 eV；含氢缺陷模型计算结果得到3 526 cm-1和3 198 cm-1的拉曼峰与柯石英的合成实验结果基本符合.FTIR分析表明石马地区柯石英结构水含量具有不均一性；模拟计算得到（4H）Si复合缺陷模型比（AlH）Si有更低的复合缺陷形成能，有更加稳定的结构，柯石英结构水中（OH）4$ \Leftrightarrow $Si氢结合机制是优先模式，为实验研究提供理论依据.Abstract: The study of the distribution of structural water at microscopic scale can provide important evidences for the formation environment and tectonic evolution dynamics of UHP metamorphic rocks.In order to investigate the distribution characteristics and the relationship between occurrence state and microstructure defects of "nominal anhydrous minerals" (NAMs) structure water in ultrahigh pressure metamorphic rocks from Dabie Mountains, the NAMs such as coesite in eclogites of the Shima area from Dabie Mountains were studied by FTIR analysis and first-principle calculations. FTIR studies show that the main absorption peaks of coesite are (Ⅰ) 3 561-3 580 cm-1, (Ⅱ) 3 433-3 462 cm-1 and (Ⅲ) 3 412-3 425 cm-1 respectively. The structural water content of the coesites in Shima is 15×10-6-52×10-6, with an average of 32×10-6. The vacancy formation energies of the (4H)Si and (AlH)Si complex defect coesite supercells (2×1×1) calculated by the first principle are -4.92 eV and -3.10 eV respectively. The Raman peaks at 3 526 and 3 198 cm-1 in the hydrogen-containing defect models of coesite are consistent with the experimental results. The vacancy defect formation energy of the (4H)Si complex defect model is lower, which is the more stable structure than (AlH)Si. Moreover, the (OH)4$ \Leftrightarrow $Si hydrogen bonding mechanism is a preferential model, which provides the theoretical basis for the experimental research.
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Key words:
- coesite /
- structural water /
- infrared spectroscopy /
- first-principle calculation /
- mineralogy
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图 1 大别山地区岩石构造单元图
据董火根和郭振宇(1996).1.各构造单元(Ⅰ.北大别岛弧杂岩；Ⅱ.中大别碰撞杂岩；Ⅲ.南大别活化盖层和扬子大陆基底；Ⅳ.古生界弧后盆地；Ⅴ.扬子大陆前陆逆掩带)；2.超高压变质岩；3.镁铁-超镁铁质岩；4.中生代花岗岩基；5.晚中生代碱性花岗岩；6.主要断裂带
Fig. 1. Tectonic units in Dabie Mountains
图 2 榴辉岩中柯石英的显微光学照片
Omp.绿辉石；Coe.柯石英；Qtz.石英；Grt.石榴石
Fig. 2. Microphotograph of coesite in eclogites
图 3 石马地区柯石英的典型红外光谱图
Fig. 3. Representative IR spectra of coesite samples from Shima area
图 4 (a)和(b)分别代表柯石英(4H)Si、(AlH)Si复合缺陷超晶胞模型(2×1×1)
黄色、红色、白色和紫色分别代表Si、O、H和Al原子
Fig. 4. Defective crystals containing (4H)Si (a), (AlH)Si (b) vacancies in coesite (2×1×1) supercell
图 5 柯石英(4H)Si和(AlH)Si缺陷模型理论计算的拉曼光谱图
Fig. 5. Theoretical Raman spectra of (4H)Si and (AlH)Si defect in coesite
表 1 大别山石马地区柯石英的红外光谱分析结果
Table 1. FTIR analysis of coesite in Shima area of Dabie Mountains, China
样品 厚度(mm) 位置 组Ⅰ(3 561~3 580 cm-1) 组Ⅱ(3 433~3 462 cm-1) 组Ⅲ(3 412~3 425 cm-1) 结构水含量(10-6) 强度 FWHH Area 强度 FWHH Area 强度 FWHH Area SM-1 0.140 C 0.187 61.87 12.330 - - - 0.257 77.29 4.72 52±(3) R 0.223 39.37 9.330 0.057 25.67 1.57 - - - 15±(1) SM-2 0.210 C 0.110 90.29 9.820 0.045 53.71 2.60 0.076 68.02 6.56 33±(2) R 0.082 44.36 3.290 0.062 48.75 2.82 0.064 44.64 3.23 28±(2) SM-3 0.100 C 0.053 17.36 1.028 0.057 34.71 12.41 0.058 30.77 2.56 27±(2) R 0.075 87.68 7.770 - - - 0.068 28.79 4.80 38±(2) 
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表 2 理想情况、(4H)Si、(AlH)Si含氢缺陷的柯石英分别对应的超晶胞能量及复合缺陷形成能
Table 2. Total energy, vacancy formation energy of ideal model, (4H)Si and (AlH)Si hydrogen complex defects coesite supercells
模型 E(eV) δE(eV) 理想 -31 137.13 - (4H)Si -31 090.15 -4.92 (AlH)Si -31 104.50 -3.10
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