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Caractérisation de paires d’ions par spectroscopies IR, UV et rayons X, interprétées par calculs de chimie quantique

Jeremy Donon 1, 2
2 SBM - Structures BioMoléculaires
IRAMIS - Institut Rayonnement Matière de Saclay, LIDyl - Laboratoire Interactions, Dynamiques et Lasers (ex SPAM)
Abstract : Ion pairs are ubiquitous in nature, from sea water, aerosols, to living organisms. They influence the properties of concentrated ion solutions, and thus play a crucial role in various chemical reactions and biological processes. However, the characterization of ion pairs faces some difficulties: on one hand, several types of pairs coexist, and on the other hand, they are transient species in solution. In this context, this work presents several studies carried out according to three main research studies, backed by an original approach in the gas phase, and then in solution. Firstly, the effects of the electric field produced by the ion pair on the UV spectroscopy of a chromophore in gas phase (Stark effects) are studied. The ion groups can produce an electric field high enough to induce significant electronic Stark effects on a nearby UV chromophore. This study is conducted on model systems (C₆H₅-(CH₂)n-COO⁻,M⁺) with M = Li, Na, K, Rb, Cs and n = 1-3, allowing to vary the electric field experienced by the UV chromophore. These different systems are studied in the gas phase by UV spectroscopy combined with quantum chemistry calculations, as well as by conformation selective IR spectroscopy. Based on the analysis of the electronic Stark effects, precise conformational assignments can be proposed for electronic transitions separated by a few cm-1, without resorting to IR spectroscopy, or frequency calculations. The next study is focused mainly on understanding the environmental effects on ion pairs by microsolvation experiments in gas phase. The pair of sodium acetate ions [CH₃-COO⁻,Na⁺] is studied for the first time in a trimer complex with p-xylene by IR spectroscopy. Microhydration experiments are then carried out on charged ion pairs ([CH₃-COO⁻,M²⁺]; M = Ca, Ba), highlighting two different behaviours depending on the nature of the cation. The final research is to detect and identify the structures formed by the ions in electrolytic solutions by IR and RX spectroscopy. The first experiment is carried out on electrolytic solutions ([CH₃-COO⁻,M⁺]; M = Li, Na and K) by TF-IR spectroscopy by varying the ion concentration. A theoretical study is then carried out in order to propose a theoretical spectrum for each type of pair, and to confront them with experimental spectra in solution. The approach is based on the calculation of the IR signature of pairs ([CH₃-COO⁻,M⁺]; M = Li, Na, K, Rb and Cs) and free anion in solution, where the first solvation layer were described at the quantum level, followed by a solvent continuum. For each type of pair, spectroscopic families, consistent with the experimental data, are identified. This original approach paves way to the identification of supramolecular structures in electrolytic solutions. Finally, the first FZRET experiment in liquid micro-jet is carried out on a potassium acetate solution, providing access to a measurement of the distance distribution between cations and paired anions.In these studies, different methods are used ranging from experiment to theory, from the gas phase to solution. This work illustrates the need to combine several methods in order to obtain additional data and allow a better characterization of the supramolecular organisation of ions and their environment.
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Jeremy Donon. Caractérisation de paires d’ions par spectroscopies IR, UV et rayons X, interprétées par calculs de chimie quantique. Chimie théorique et/ou physique. Université Paris-Saclay, 2020. Français. ⟨NNT : 2020UPASS106⟩. ⟨tel-02922344⟩

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