关于重型动因体中的共价结合的起源
Morgan P Kelley1, Jing Su1, Matthew Urban2
1Theoretical Division, Los Alamos National Laboratory , Los Alamos, New Mexico 87545, United States.
Journal of the American Chemical Society
|June 29, 2017
概括
由于5f轨道能量与配体的退化,重型动因化合物表现出增加的共价性. 这表明能量匹配, 不仅仅是重叠,
科学领域:
- 无机化学
- 乙化物化学
- 计算化学
背景情况:
- 晚期活性化物比早期活性化物具有更大的共价性,但根本原因尚不清楚.
- 了解这种转变对于预测和操纵行为是至关重要的.
研究的目的:
- 调查重型动因化合物中增加的共价相互作用的来源.
- 分析动因二聚酸复合物以确定影响共价性的因素.
主要方法:
- 检查了活性二聚酸盐复合物的稳定常数.
- 相关稳定性与行为体5f轨道和联体分子轨道之间的能量退化.
主要成果:
- 与较轻的 (Am,Cm) 相比,较重的活性化物 (Bk,Cf) 的稳定常数略有增加.
- 发现Bk和Cf的An5f轨道和二聚酸分子轨道之间的能量退化显著增加.
- 确定了轨道混合, 导致共价,
结论:
- 沉重的行为体中增加的协同性来自于它们的5f轨道与连接器轨道的退化.
- 能量退化,而不是空间轨道重叠,是这些系统中共价的主要驱动因素.
- 由于它们的5f轨道特征,重型活性物非常适合研究能量退化驱动的共价性.
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