Structure, Vibrational Spectra and (11)B-NMR Chemical Shift of Na8[AlSiO4]6(B(OH)4)2: Comparison of Theory and Experiment.
Structure, Vibrational Spectra and (11)B-NMR Chemical Shift of Na8[AlSiO4]6(B(OH)4)2: Comparison of Theory and Experiment.
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DOI：
10.1021/acs.jpca.6b06508
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发表时间：
2016-09
期刊：
影响因子：
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通讯作者：
Alexander G Schneider;Lars Schomborg;Anna C. Ulpe;C. Rüscher;T. Bredow
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文献类型：
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作者：
Alexander G Schneider;Lars Schomborg;Anna C. Ulpe;C. Rüscher;T. Bredow
采用密度泛函理论（DFT）方法，在广义梯度近似（GGA）水平上对四羟基硼酸盐方钠石Na 8 [AlSiO 4]6（B（OH）4）2的红外和拉曼振动光谱进行了理论解释，对（11）B-NMR化学位移进行了归属，并对其结构进行了计算.对插层化合物进行了优化，得到了B（OH）4（-）的结构参数：B-O-B（105.3-115.3°）和B-O-H（111.5-115.4°）角，B-O（1.476 nm，1.491 nm）和O-H（0.98 nm）距离。将计算得到的简正模归属于实验得到的红外和拉曼光谱。在一般情况下，理论和实验之间的密切协议。平均绝对偏差（MAD）小于11 cm（-1）。我们还计算了Na 8 [AlSiO 4]6（B（OH）4）2相对于Na 8 [AlSiO 4]6（BH 4）2在四氢硼酸盐水合反应中的结晶稳定性。
Density functional theory (DFT) calculations at generalized gradient approximation (GGA) level were performed to interpret experimental IR and Raman vibrational spectra, to assign (11)B-NMR chemical shifts, and to calculate the structure of the tetrahydroxyborate sodalite Na8[AlSiO4]6(B(OH)4)2. Full optimization of the intercalated compound gave the following structural parameters of B(OH)4(-): B-O-B (105.3-115.3°) and B-O-H (111.5-115.4°) angles, B-O (1.476 Å, 1.491 Å) and O-H (0.98 Å) distances. The calculated normal modes were assigned to experimental IR and Raman spectra. In general, close agreement between theory and experiment was obtained. The mean absolute deviation (MAD) is below 11 cm(-1). We also calculate the thermodynamical stability of Na8[AlSiO4]6(B(OH)4)2 with respect to Na8[AlSiO4]6(BH4)2 in the context of the tetrahydroborate hydration reaction.