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首页> 外文期刊>Zeitschrift fur Naturforschung. A, A journal of physical sciences >Motion of Water Molecules and Hydrogen Bonds in Zinc Hexachlorostannate(Ⅳ) Hexahydrate as Studied by ~1H NMR and ~(35)Cl NQR
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Motion of Water Molecules and Hydrogen Bonds in Zinc Hexachlorostannate(Ⅳ) Hexahydrate as Studied by ~1H NMR and ~(35)Cl NQR

机译：〜1H NMR和〜（35）Cl NQR研究六氯锡酸锌（Ⅳ）六水合物中水分子和氢键的运动

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摘要

The ~1H NMR spin-lattice relaxation time T_1, ~(35)Cl NQR frequency ν_Q, and ~(35)Cl NQR spin-lattice relaxation time T_(1Q) of [Zn(H_2O)_6] [SnCl_6] (zinc hexachlorostannate(Ⅳ) hexahydrate) have been measured at temperatures between 77 and 350 K. The NQR spin echo signal with ν_Q = 15.689 MHz at 77 K showed a positive temperature coefficient attributable to O-H-Cl type H-bonds in the crystal. ν_Q at 77 K is strongly correlated with the electronegativity χ_M of the metal M in the series of stannates [M(H_2O)_6] [SnCl_6] (M = Mg, Ca, Mn, Co, Ni, Zn). A T_1 minimum observed for the Zn salt is ascribed to 180° flips of water molecules with an activation energy of 20 kJ mol~(-1). The motion is influenced by repulsive forces among the water molecules within a cation rather than by attractive forces between the H-bonded H and Cl atoms. T_(1Q), proved to be mainly governed by lattice vibrations, weakly modulated by the fluctuating electric field gradient caused by the 180° flip motions.
机译：[Zn（H_2O）_6] [SnCl_6]（六氯锡酸锌）的〜1H NMR自旋晶格弛豫时间T_1，〜（35）Cl NQR频率ν_Q和〜（35）Cl NQR自旋晶格弛豫时间T_（1Q） （Ⅳ）六水合物）在77至350 K之间的温度下进行了测量。在77 K时ν_Q= 15.689 MHz的NQR自旋回波信号显示出正温度系数，可归因于晶体中的OH-Cl型H键。 77 K处的ν_Q与锡酸盐系列[M（H_2O）_6] [SnCl_6]（M = Mg，Ca，Mn，Co，Ni，Zn）中金属M的电负性χ_M密切相关。锌盐的T_1最小值归因于水分子的180°翻转，其活化能为20 kJ mol〜（-1）。该运动受阳离子内水分子之间的排斥力的影响，而不是受与H键合的H和Cl原子之间的吸引力的影响。 T_（1Q）被证明主要受晶格振动控制，而由180°翻转运动引起的波动电场梯度对其进行弱调制。

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