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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Spectroscopy and photochemistry of sodium chromate ester cluster ions
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Spectroscopy and photochemistry of sodium chromate ester cluster ions

机译：铬酸钠酯簇离子的光谱学和光化学

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摘要

In the present study, we investigate the spectroscopy and photochemical behavior of chromate ester cluster ions in vacuo in the visible and near-UV. Chromate ester cluster ions Na_n[CrO_3(OCH _3)]_(n+1) - (n = 1, 2) are generated by electrospray ionization of sodium dichromate in water and methanol. Upon irradiation with photon energies between 2 and 5.6 eV, dissociation occurs. The photodissociation spectra of these ions are very similar to the UV/vis absorption spectra of the sample solution with solvatochromic shifts less than 0.1 eV. The electronic excitations in this photon energy range are assigned to ligand-to-metal charge transfer from the oxygen ligands to the chromium within the chromate ester. Fragment channels corresponding to intracluster reactions involving reduction of the metal centers as well as evaporative processes leading to the loss of a neutral Na[CrO_3(OCH_3)] salt unit are observed. The results are discussed in the framework of organometallic redox mechanisms and density functional theory.
机译：在本研究中，我们研究了可见光和近紫外光下铬酸酯簇离子在真空中的光谱和光化学行为。铬酸酯簇离子Na_n [CrO_3（OCH _3）] _（n + 1）-（n = 1，2）通过重铬酸钠在水和甲醇中的电喷雾电离产生。用2至5.6 eV之间的光子能量照射时，发生离解。这些离子的光解离光谱与样品溶液的色变位移小于0.1 eV的UV / vis吸收光谱非常相似。在此光子能量范围内的电子激发被分配给从氧配体到铬酸酯中铬的配体到金属的电荷转移。观察到片段通道对应于簇内反应，该片段内反应涉及金属中心的还原以及蒸发过程，导致中性Na [CrO_3（OCH_3）]盐单元的损失。在有机金属氧化还原机理和密度泛函理论的框架内讨论了结果。

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