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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical study of the structural properties of plutonium(IV) and (VI) complexes
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Theoretical study of the structural properties of plutonium(IV) and (VI) complexes

机译：IV（IV）和（VI）配合物结构性质的理论研究

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The structural properties of several plutonium(IV) and (VI) complexes have been examined in the gaseous and aqueous phases using Kohn-Sham density functional theory calculations with scalar relativistic effective core potentials and the polarizable continuum solvation model. The aquo and nitrate complexes of PuO 2 ~(2+) and Pu ~(4+) were considered in addition to the aquo-chloro complexes of PuO 2 ~(2+). The nitrate and chloro- complexes formed with triphenylphosphine oxide (TPPO) and tributylphosphate (TBP) respectively were also studied. The structural parameters of the plutonyl complexes were compared to their uranyl and neptunyl analogues. The bond lengths and vibrational frequencies of the plutonyl complexes can generally be computed with sufficient accuracy with the pure PBE density functional with shorter bond lengths being predicted by the B3LYP functional. The structural parameters of the [PuO _2Cl _2L _2] systems formed with TPPO and TBP as well as the aqueous [PuO _2Cl _2(H _2O) _3] complex are matched to previous experimental results. Overall, the inclusion of ligands in the equatorial region results in significant changes in the stretching frequency of the plutonyl group. The structural features of the plutonyl (VI) systems are rather similar to those of their 5f ~0 uranyl and 5f ~1 neptunyl counterparts. For the Pu(IV) aquo and nitrate complexes, the average of the calculated Pu-OH _2 and Pu-O nitrate bond lengths are generally within 0.04 ? of the reported experimental values. Overall Kohn-Sham DFT can be used successfully in predicting the structures of this diverse set of Pu(VI) and Pu(IV) complexes.
机译：已使用Kohn-Sham密度泛函理论计算，标量相对论有效核心电位和可极化连续体溶剂化模型对气相和水相中几种several（IV）和（VI）配合物的结构性质进行了研究。除PuO 2〜（2+）的水-氯配合物外，还考虑了PuO 2〜（2+）和Pu〜（4+）的水和硝酸配合物。还研究了分别由三苯膦氧化物（TPPO）和磷酸三丁酯（TBP）形成的硝酸盐和氯盐配合物。将the酰基复合物的结构参数与其铀酰和海and基类似物进行比较。通常，在纯PBE密度官能团具有足够的准确性的情况下，素复合物的键长和振动频率通常可以以足够的精度计算，而B3LYP官能团可以预测较短的键长。由TPPO和TBP以及[PuO _2Cl _2（H _2O）_3]水溶液形成的[PuO _2Cl _2L _2]系统的结构参数与先前的实验结果相符。总体而言，在赤道区域中包含配体会导致p酰基的拉伸频率发生重大变化。 lu酰基（VI）系统的结构特征与其5f〜0铀酰和5f〜1庚基类似物的结构特征非常相似。对于Pu（IV）水和硝酸盐配合物，计算得出的Pu-OH _2和Pu-O硝酸盐键长的平均值通常在0.04？报告的实验值。总体而言，Kohn-Sham DFT可以成功地用于预测这种多样化的Pu（VI）和Pu（IV）配合物的结构。

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