The effect of metal cations on the nature of the first electronic transition of liquid water as studied by attenuated total reflection far-ultraviolet spectroscopy.
The effect of metal cations on the nature of the first electronic transition of liquid water as studied by attenuated total reflection far-ultraviolet spectroscopy.
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通过衰减全反射远紫外光谱研究金属阳离子对液态水第一次电子跃迁性质的影响。
DOI：
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发表时间：
2012
期刊：
影响因子：
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通讯作者：
Y. Ozaki
中科院分区：
文献类型：
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作者：
Takeyoshi Goto;A. Ikehata;Y. Morisawa;N. Higashi;Y. Ozaki
通过分析第I、II和XIII族金属硝酸盐电解质溶液的衰减全反射远紫外（ATR-FUV）光谱，从阳离子水合的角度研究了液态水的第一电子跃迁（<$X射线）。1 M电解质溶液的<$X射线跃迁能（Li（+）：8.024 eV和Cs（+）：8.013 eV）高于纯水（8.010 eV），并与阳离子水合的吉布斯自由能线性相关。<$X射线跃迁能的增加主要归因于阳离子的存在引起的基态水分子的氢键形成能。对于高电荷密度的阳离子H（+）、Li（+）和Be（2+），观察到偏离线性关系，这反映了激发态的电子能量也受到扰动。量子化学计算表明，水-阳离子复合物的<$X →跃迁能依赖于阳离子的水合结构。计算的水分子水合高电荷密度阳离子的<$X射线跃迁能比低电荷密度阳离子的跃迁能分布得更广。计算的水-阳离子复合物的跃迁能谱与ATR-FUV光谱测量的<$X射线跃迁带的宽度直接相关。
The first electronic transition (Ã←X̃) of liquid water was studied from the perspective of the hydration of cations by analyzing the attenuated total reflection far-ultraviolet (ATR-FUV) spectra of the Group I, II, and XIII metal nitrate electrolyte solutions. The Ã←X̃ transition energies of 1 M electrolyte solutions are higher (Li(+): 8.024 eV and Cs(+): 8.013 eV) than that of pure water (8.010 eV) and linearly correlate with the Gibbs energies of hydration of the cations. The increases in the Ã←X̃ transition energies are mostly attributable to the hydrogen bond formation energies of water molecules in the ground state induced by the presence of the cations. The deviation from the linear relation was observed for the high charge density cations, H(+), Li(+), and Be(2+), which reflects that the electronic energies in the excited states are also perturbed. Quantum chemical calculations show that the Ã←X̃ transition energies of the water-cation complexes depend on the hydration structures of the cations. The calculated Ã←X̃ transition energies of the water molecules hydrating high charge density cations spread more widely than those of the low charge density cations. The calculated transition energy spreads of the water-cation complexes directly correlate with the widths of the Ã←X̃ transition bands measured by ATR-FUV spectroscopy.
影响因子：
15
作者：
Hribar, B;Southall, NT;Dill, KA
通讯作者：
Dill, KA