Probing Chemical Bonding and Electronic Structures in ThO− byAnion Photoelectron Imaging and Theoretical Calculations
Probing Chemical Bonding and Electronic Structures in ThO− byAnion Photoelectron Imaging and Theoretical Calculations
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通过阴离子光电子成像和理论计算探测 ThO- 中的化学键和电子结构
DOI：
10.1021/acs.jpca.6b11554
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Hongtao Liu
中科院分区：
文献类型：
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作者：
Yanli Li;Jinghan zou;Xiao-Gen Xiong;Jing Su;Hua Xie;Zejie Fei;Zichao Tang;Hongtao Liu
由于对钍基熔盐反应堆的新研究，人们对增强钍化学实验和理论知识的需求和兴趣不断增长。与铀相比，钍迄今为止的化学研究报道较少。在这里，我们报告了一氧化钍阴离子的振动分辨光电子成像。 ThO 的电子亲和势首次报道为 0.707 ± 0.020 eV。 ThO 分子及其阴离子的振动频率由 Franck-Condon 模拟确定。获得了 ThO– 中双电子跃迁的光谱证据，表明 ThO– 中的 (7sσ)2(6dδ)1 电子和 ThO 中的 (7sσ)2 电子之间存在强电子相关性。这些发现可以通过使用包括自旋轨道耦合在内的量子化学计算来解释，并分析气态 ThO 分子的化学键。目前的工作将丰富我们对 6d 价壳键合能力的理解。
Because of renewed research on thorium-based molten salt reactors, there is growing demand and interest in enhancing the knowledge of thorium chemistry both experimentally and theoretically. Compared with uranium, thorium has few chemical studies reported up to the present. Here we report the vibrationally resolved photoelectron imaging of the thorium monoxide anion. The electron affinity of ThO is first reported to be 0.707 ± 0.020 eV. Vibrational frequencies of the ThO molecule and its anion are determined from Franck–Condon simulation. Spectroscopic evidence is obtained for the two-electron transition in ThO–, indicating the strong electron correlation among the (7sσ)2(6dδ)1electrons in ThO–and the (7sσ)2electrons in ThO. These findings are explained by using quantum-chemical calculations including spin–orbit coupling, and the chemical bonding of gaseous ThO molecules is analyzed. The present work will enrich our understanding of bonding capacities with the 6d valence shell.