Calculation of Dipole-Forbidden 5f Absorption Spectra of Uranium(V) Hexa-Halide Complexes,The Journal of Physical Chemistry Letters

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Calculation of Dipole-Forbidden 5f Absorption Spectra of Uranium(V) Hexa-Halide Complexes
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2018-02-08 00:00:00 , DOI: 10.1021/acs.jpclett.7b03441
Yonaton N. Heit ₁ , Frédéric Gendron ₁ , Jochen Autschbach ₁

Affiliation

Restricted-active-space wave function calculations including spin–orbit coupling, in combination with Kohn–Sham density functional calculations of vibrational modes, were used to determine the vibronic and electronic absorption intensities of the near-infrared electric dipole-forbidden 5f–5f transitions of representative uranium(V) hexa-halide complex ions. The agreement with experimentally assigned vibronic and electronic transitions measured for powder or solution samples of salts of the complex ions is reasonable overall and excellent for the experimentally best-resolved E_5/2u → E_5/2u^′ bands. The intensity of the vibronic transitions may be borrowed from ligand-to-metal charge-transfer excitations as well as 5f-to-6d metal-centered transitions. Magnetically allowed electronic transitions contribute to the two lower-frequency bands of the ligand-field spectrum.

中文翻译：

铀（V）六卤化物配合物的偶极子禁态5f吸收光谱的计算

包括自旋-轨道耦合在内的受限活动空间波函数计算，与振动模式的Kohn-Sham密度函数计算相结合，用于确定近红外电偶极禁止的5f-5f跃迁的振动和电子吸收强度代表性的铀（V）六卤化物络合物离子。对于复合离子盐的粉末或溶液样品测量的与实验分配的振动和电子跃迁相吻合，这在总体上是合理的，并且对于实验上最佳分辨的E _{5/2 u} → E _{5/2 u}^'而言是极好的。乐队。可以从配体到金属的电荷转移激发以及从5f到6d的以金属为中心的跃迁中借用电子振动跃迁的强度。磁性允许的电子跃迁有助于配体场谱的两个较低频段。

更新日期：2018-02-08

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