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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Infrared spectroscopy of discrete uranyl anion complexes
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Infrared spectroscopy of discrete uranyl anion complexes

机译：离散的铀酰阴离子配合物的红外光谱

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摘要

The Free-Electron Laser for Infrared Experiments (FELIX) was used to study the wavelength-resolved multiple photon photodissociation of discrete, gas-phase uranyl (UO22+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO(2)A(S)(n)](+), where A was hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO(2)A](+)) were as low or lower than measurements for [UO2](2+) ligated with as many as five strong neutral donor ligands and are comparable to solution-phase values. This result was surprising because initial DFT calculations predicted values that were 30-40 cm(-1) higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO(2)A](+) produced [UO(2)AS](+), which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO(2)AS](+) were in accord with trends in the data and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared. for [UO(2)AS](+) species having different solvent neutrals, values decreased with increasing neutral nucleophilicity.
机译：用于红外实验的自由电子激光（FELIX）用于研究具有单个阴离子配体（A），带有或不带有连接溶剂分子（S）的离散气相铀酰（UO22 +）络合物的波长分辨多光子光解离）。测量具有通式[UO（2）A（S）（n）]（+）的配合物的铀酰抗对称和对称拉伸频率，其中A为氢氧化物，甲醇盐或乙酸盐; S为水，氨，丙酮或乙腈;并且n = 0-3。仅与阴离子（[UO（2）A]（+）结合的铀酰的抗对称拉伸频率的值比与多达五个强中性供体的[UO2]（2+）的测量值低或低。配体与溶液相值相当。此结果令人惊讶，因为初始DFT计算预测的值比直觉高30-40 cm（-1），与数据一致。修改基集并使用其他功能可以提高甲醇盐和乙酸盐配合物的计算精度，但是无论使用哪种计算方法，氢氧化物的计算值均大于测量值。中性供体配体S附着到[UO（2）A]（+）产生了[UO（2）AS]（+），它仅对铀酰抗对称拉伸频率产生非常适度的变化，并且没有普遍改变频率降低值。 [UO（2）AS]（+）的DFT计算与数据趋势一致，表明通过弱化U-阴离子键和铀酰可以适应溶剂的附着。比较了铀酰频率。对于具有不同溶剂中性的[UO（2）AS]（+）物种，其值随中性亲核性的增加而降低。

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