A neutron scattering study of strong symmetric hydrogen bonds in potassium and cesium hydrogen bistrifluoroacetates: Determination of the crystal structures and of the single-well potentials for protons

François Fillaux (1) , Alain Cousson (2) , Juan F. R. Archilla (3) , John Tomkinson (4)

1 LADIR - Laboratoire de Dynamique Interactions et Réactivité
2 LLB - UMR 12 - Laboratoire Léon Brillouin
3 Group of nonlinear physics
4 RAL - STFC Rutherford Appleton Laboratory

The crystal structures of potassium and cesium bistrifluoroacetates, KH(CF$_3$COO)$_2$ and CsH(CF$_3$COO)$_2$, respectively, were determined at room and cryogenic temperatures with the single crystal neutron diffraction technique. The crystals belong to the monoclinic space groups, $I2/a$ and $A2/a$, respectively, and there is no evidence of any structural phase transition. In both crystals, trifluoroacetate entities in centrosymmetric dimers are linked by very short hydrogen bonds lying across a center of inversion. The thermal parameters provide no evidence of any double minimum potential for hydrogen bond protons. Single-minimum potentials were determined via best fitting to the inelastic neutron scattering spectral profiles of the stretching vibrations. They comprise a narrow well for the ground state and a very broad quasi-harmonic well for excited states. The spread out of the wave functions of these states shows that protons are no longer confined between the oxygens. Presumably, they are attracted by the lone-pairs of oxygen atoms. These potential emphasize the covalent nature of the OO bond and the ionic character of the hydrogen bond proton.

Domaines: Chimie théorique et/ou physique

François Fillaux, Alain Cousson, Juan F. R. Archilla, John Tomkinson. A neutron scattering study of strong symmetric hydrogen bonds in potassium and cesium hydrogen bistrifluoroacetates: Determination of the crystal structures and of the single-well potentials for protons. Journal of Chemical Physics, 2008, 128, pp.205402. ⟨10.1063/1.2927353⟩. ⟨hal-00294001⟩