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

Dumitru-Claudiu Sergentu 1, 2 Florent Réal 3 Gilles Montavon 1 Nicolas Galland 2 Rémi Maurice 1
1 SUBATECH - Laboratoire SUBATECH Nantes
2 CEISAM - Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation
3 PCMT - Physico-Chimie Moléculaire Théorique
PhLAM - Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523
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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http://hal.in2p3.fr/in2p3-01447927
Contributor : Rémi Maurice <>
Submitted on : Friday, January 27, 2017 - 1:21:17 PM
Last modification on : Wednesday, November 20, 2019 - 3:16:26 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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