Actinyl cation-cation interactions in the gas phase: an accurate thermochemical study

Feng Rulin; Glendening Eric D.; Peterson Kirk A.

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Actinyl cation-cation interactions in the gas phase: an accurate thermochemical study

机译：气相中的阳极阳离子阳离子相互作用：准确的热化学研究

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Gas phase actinyl cation-cation interactions (CCIs) were studied by an accurate composite coupled cluster thermochemical approach for the first time. A number of CCI dimers were constructed from the monomers UO22+, UO2+, NpO22+, NpO2+, PuO2+, and AmO2+. All CCI dimers studied were calculated to be thermodynamically unstable, with dissociation energies ranging from -60 to -90 kcal mol(-1), but in many cases kinetic stability was indicated by calculated local minima with well depths as large as approximate to 15 kcal mol(-1). Most of the dimers studied involved a T-shaped geometry, although one side-on dimer, (UO2+)(2), was included since it was amenable to coupled cluster methods. In the T-shaped isomers the most stable dimers were calculated to arise when the oxo-group of an An(v) actinyl cation was oriented towards the metal center of an An(vi) actinyl cation. For both mixed-valent An(vi)/An(v) and mono-valent An(v) dimers, the stability as estimated from the depth of the calculated local minimum decreased in the donor series U(v) > Np(v) > Pu(v) > Am(v). These trends correlate well with experimental trends in condensed phase CCIs. A rationale for the bonding in CCIs was investigated by carrying out charge transfer analyses using the natural bond orbital (NBO) method. Augmenting the usual Lewis acid-base explanation, CCIs are the direct result of a competition between charge transfer stabilization, which can be as much as 0.11e or 30.7 kcal mol(-1) at equilibrium, and Coulombic repulsive destabilization.

机译：通过第一次通过精确的复合偶联的聚类热化学方法研究气相抗阳离子阳离子相互作用（CCIS）。从单体UO 2 2 +，UO 2 +，NPO22 +，NPO2 +，PUO2 +和amo2 +构建了许多CCI二聚体。所研究的所有CCI二聚体都是热力学上不稳定的，该解离能量在-60至-90千卡摩尔（-1）中，但在许多情况下，通过计算局部最小值来表示动力学稳定性，具有大约15 kcal的良好深度的局部最小值。 mol（-1）。所研究的大多数二聚体涉及T形几何形状，尽管包括一个侧面二聚体（UO2 +）（2），因为它适用于偶联的簇方法。在T形异构体中，计算最稳定的二聚体以产生当氧代 - 基团的辐射胶阳离子朝向（VI）挥发阳离子的金属中心取向时出现。对于混合价AN（VI）/ AN（V）和单体（V）（V）二聚体，从计算出的局部最小值深度估计的稳定性在供体系列U（V）> NP（V）中降低> PU（v）> am（v）。这些趋势与凝聚相CCIS的实验趋势相比良好。通过使用天然键（NBO）方法进行电荷转移分析来研究CCIS中键合的理由。增强通常的路易斯酸碱解释，CCI是电荷转移稳定化之间竞争的直接结果，可以在平衡和库仑排斥稳定性下均多为0.11e或30.7克尔（-1）。

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《Physical chemistry chemical physics: PCCP》 |2019年第15期|共12页
作者
Feng Rulin; Glendening Eric D.; Peterson Kirk A.;
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Washington State Univ Dept Chem Pullman WA 99164 USA;

Indiana State Univ Dept Chem Terre Haute IN 47809 USA;

Washington State Univ Dept Chem Pullman WA 99164 USA;

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正文语种 eng
中图分类物理学;化学;
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Actinyl cation-cation interactions in the gas phase: an accurate thermochemical study

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