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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >First Principles Simulation of the Bonding, Vibrational, and Electronic Properties of the Hydration Shells of the High-Spin Fe~(3+) Ion in Aqueous Solutions
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First Principles Simulation of the Bonding, Vibrational, and Electronic Properties of the Hydration Shells of the High-Spin Fe~(3+) Ion in Aqueous Solutions

机译：高自旋Fe〜（3+）离子在水溶液中水合壳的键合，振动和电子性质的第一性原理模拟

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摘要

Results of parameter-free first principles simulations of a spin up 3d~5 Fe~(3+) ion hydrated in an aqueous solution (64 waters, 30 ps, 300 K) are reported. The first hydration shell associated with the first maximum of the radial distribution function, gFeO(r), at d(Fe-O_I)= 2.11-2.15 A, contains 6 waters with average d(OH)=0.99 A, in good agreement with observations. A second shell with average coordination number 13.3 can be identified with average shell radius of d(Fe-O_II)=4.21-4.32 A. The waters in this hydration shell are coordinated to the first shell via a trigonal H-bond network with d(O_I-O_II)=2.7-2.9 A, also in agreement with experimental measurements. The first shell tilt angle average is 33.4° as compared to the reported value of 41°. Wannier-Boys orbitals (WBO) show an interaction between the unoccupied 3d orbitals of the Fe~(3+) valence (spin up, 3d~5) and the occupied spin down lone pair orbitals of first shell waters. The effect of the spin ordering of the Fe~(3+) ion on the WBO is not observed beyond the first shell. From this local bond analysis and consistent with other observations, the electronic structure of waters in the second shell is similar to that of a bulk water even in this strongly interacting system. H-bond decomposition shows significant bulk-like structure within the second shell for Fe~(3+). The vibrational density of states shows a first shell red shift of 230 cm~(-1) for the V1,2_(V2),V3 overtone, in reasonable agreement with experimental estimates for trivalent cations (300 cm~(-1)). No exchanges between first and second shell were observed. Waters in the second shell exchanged with bulk waters via dissociative and associative mechanisms. Results are compared with an AIMD study of Al~(3+) and 64 waters. For Fe~(3+) the average first shell tilt angle is larger and the tilt angle H-bond decomposition shows that second shell to second shell H-bonding is enhanced in Fe~(3+) suggesting andistribution wider.earlier onset of bulk-like water structure.
机译：报道了在水溶液（64个水，30 ps，300 K）中水合的自旋3d〜5 Fe〜（3+）离子的无参数第一原理模拟结果。与径向分布函数的第一最大值gFeO（r）关联的第一个水化壳在d（Fe-O_I）= 2.11-2.15 A时包含6个平均d（OH）= 0.99 A的水，与观察。可以确定平均配位数为13.3的第二壳，其平均壳半径为d（Fe-O_II）= 4.21-4.32A。该水化壳中的水通过具有d（ O_I-O_II）= 2.7-2.9 A，也与实验测量值一致。第一壳体倾斜角平均值为33.4°，而报告值为41°。 Wannier-Boys轨道（WBO）显示了Fe〜（3+）价的未占据3d轨道（旋转3d〜5）与第一壳水域占据的自旋向下孤对轨道之间的相互作用。 Fe〜（3+）离子在WBO上自旋有序化的影响未在第一个壳层之外观察到。从该局部键分析并与其他观察结果一致，即使在这种强相互作用的系统中，第二壳层中的水的电子结构也类似于散装水的电子结构。 H键分解显示Fe〜（3+）在第二壳层内具有明显的块状结构。状态的振动密度显示V1,2_（V2），V3泛音的第一个壳红移为230 cm〜（-1），与三价阳离子的实验估计值（300 cm〜（-1））合理吻合。没有观察到第一壳和第二壳之间的交换。第二壳中的水通过分离和缔合机制与大量水交换。将结果与AIMD对Al〜（3+）和64种水的研究进行比较。对于Fe〜（3+），平均第一壳倾斜角较大，倾斜角H键分解表明Fe〜（3+）中第二壳至第二壳H键增强，表明其分布较宽。般的水结构。

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