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Unraveling the hydration-induced ground-state change of AtO+ by relativistic and multiconfigurational wave-function-based methods

Abstract : 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 1Σ+ 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 natures of the low-lying SOF and SOC states when the hydration sphere of AtO+ is stepwise increased, with 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 3Σ and the closed-shell component of 1Δ, 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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Submitted on : Thursday, December 2, 2021 - 11:10:40 AM
Last modification on : Wednesday, April 27, 2022 - 4:30:13 AM
Long-term archiving on: : Thursday, March 3, 2022 - 7:01:29 PM

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Dumitru-Claudiu Sergentu, Florent Réal, Gilles Montavon, Nicolas Galland, Rémi Maurice. Unraveling the hydration-induced ground-state change of AtO+ by relativistic and multiconfigurational wave-function-based methods. Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2016, 18, pp.32703-32712. ⟨10.1039/C6CP05028J⟩. ⟨in2p3-01447927⟩

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