期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 18, 期 48, 页码 32703-32712出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6cp05028j
关键词
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资金
- French National Agency [ANR-11-EQPX-0004, ANR-11-LABX-0018]
The AtO+ cation is one of the main chemical forms that appear in the astatine Pourbaix diagram. This form can react with closed-shell species in solution, while in the gas phase, it has a spin-triplet ground spin-orbit-free (SOF) state. Spin-orbit coupling (SOC) mixes its MS = 0 component with the (1)Sigma(+) singlet-spin component, while keeping an essentially-spin-triplet SOC ground-state. Therefore, it was suggested that AtO+ undergoes a hydration-induced ground-state change to explain its reactivity in solution with closed-shell species [J. Phys. Chem. B, 2013, 117, 5206-5211]. In this work, we track the nature of the low-lying SOF and SOC states when the hydration sphere of AtO+ is stepwise increased, using relativistic and multiconfigurational wave-function-based methods. This work clarifies previous studies by (i) giving additional arguments justifying a solvation-induced ground-state change in this system and (ii) clearly identifying for the first time the nature of the involved SOF and SOC many-electron states. Indeed, we find at the SOF level that AtO+ undergoes a ground-state reversal between (3)Sigma-and the closed-shell component of (1)Delta, which leads to an essentially-spin-singlet and closed-shell SOC ground-state. This explains the observed reactivity of AtO+ with closed-shell species in solution.
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