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Sur l'interaction eau/anion ;
les caractères structurants et déstructrants, la rupture de symétrie du nitrate

Abstract : Using a structural and a dynamical analysis, we study theoretically the solvation of the fluoride and iodide anions in water as paradigms of structure-maker and a structure-breaker respectively. Regarding structure, we observe the opposite of what is expected based on one common "structure-maker/breaker" definition (F- distorts the hydrogen (H)-bond network, while I- enhances it). Next, we turn to dynamics and calculate the water-halide anion H-bond lifetimes, the residence time and the reorientation times for a water molecule in the first hydration shell of the halides. These confirm the greater stability of the hydration shell of fluoride, induced by a stronger H-bond with water molecules, and the greater lability of water in iodide's hydration shell. Subsequently, we apply the Generalized Jump Model (GJM) for the reorientation of a water molecule in the ions' first hydration shell. For F-, we find an unusual situation, where both reorientation mechanisms (jump and diffusive) of the GJM contribute equally, which is due to the strong H-bonding inhibiting a water OH angular jump. For I-, the jump contribution dominates, reflecting the much weaker ion water H-bond. We then turn to the study of the solvation of the polyatomic nitrate in water, employing the same methods employed for the halides and using QM/MM simulations. The structural and the dynamical analyses give results similar to those found for iodide, while the GJM reveals that two different jump mechanisms are involved for a water initially H-bonded to a Ono3- : a jump to another water or to another Ono3- . Finally, we examine, using the nitrate ion's NO bond orders and charge on, solvent-induced symmetry breaking , related to the populations of certain localized valence bond states and the fast dynamics of the interconversion between them.
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Submitted on : Tuesday, February 24, 2009 - 2:54:14 PM
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  • HAL Id : tel-00363808, version 1

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Jean Boisson. Sur l'interaction eau/anion ;
les caractères structurants et déstructrants, la rupture de symétrie du nitrate. Autre. Université Pierre et Marie Curie - Paris VI, 2008. Français. ⟨tel-00363808⟩

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