Assignment of photoelectron spectra of halide-water clusters: contrasting patterns of delocalization in Dyson orbitals.
Assignment of photoelectron spectra of halide-water clusters: contrasting patterns of delocalization in Dyson orbitals.
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卤化物-水簇的光电子能谱分配：戴森轨道中离域的对比模式。
DOI：
10.1063/1.4802251
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
J. V. Ortiz
中科院分区：
文献类型：
--
作者：
O. Dolgounitcheva;V. G. Zakrzewski;J. V. Ortiz
在各种自能近似的从头算电子传播计算提供了精确的分配的光电子能谱中观察到的峰的复合物，包括一个氟或氯阴离子和两个或三个水分子。在所有四种情况下都发现了一个以上的最小结构。当卤素阴离子是Cl（-）时，前三个终态可以描述为与水分子配位的准简并（2）P氯原子。更高的最终状态由一个氯离子与一个正电荷并置组成，正电荷在水分子上离域。对于含氟阴离子的团簇，大多数最终态对应于F和O核上离域的Dyson轨道。在Dyson轨道上有各种各样的F-O σ和π成键和反键模式。低洼的光谱峰卤化物p轨道空缺或离域溶剂轨道的分配是更有效的氯离子簇比氟离子簇，其中离域的图片来自F 2 p和H2O 1b 1轨道之间的强键合相互作用。
Ab initio electron propagator calculations in various self-energy approximations provide accurate assignments of peaks observed in the photoelectron spectra of complexes that comprise a fluoride or chloride anion and two or three water molecules. More than one minimum structure is found in all four cases. When the halide anion is Cl(-), the first three final states may be described as quasi-degenerate (2)P chlorine atoms coordinated to water molecules. Higher final states consist of a chloride anion juxtaposed to a positive charge that is delocalized over the water molecules. For the clusters with fluoride anions, most of the final states correspond to Dyson orbitals that are delocalized over the F and O nuclei. A variety of F-O σ and π bonding and antibonding patterns are evident in the Dyson orbitals. The assignment of low-lying spectral peaks to halide p orbital vacancies or to delocalized solvent orbitals is more valid for the chloride clusters than for the fluoride clusters, where a delocalized picture arises from strong bonding interactions between F 2p and H2O 1b1 orbitals.