Contact:  filhol @ um2 . fr

For a decade, density functional theory (DFT) has been successfully applied to model electrochemical reactions at interfaces,¹ reproducing vibrational frequency change, phase diagram or reactivity as a function of the applied potential or electric field. But, if the modelling is correctly reproducing the experimental phenomena, the fundamental understanding of the electronic processes at the atomic level associated with electrochemical reactions is still unclear. Many approaches exist for rationalizing reactivity for both molecular and extended systems such as molecular orbital diagram, conceptual DFT (Fukui functions…), d-band centre … No such method is as much advanced in surface electrochemistry. We have shown² that Fukui function mostly gives the spatial localization of the added charge and also includes polarization effects. It quantifies the modification of molecule/surface interaction with applied potential and is at the core of the electrochemical phenomena. We also have shown that these concepts developed for electrochemistry can be extended to understand the self-organization of some surfaces and the specific reactivity of metal nanoparticle.^3,4 We will demonstrate in these cases that the specific properties arise from a surface disproportionation where a mixing of surfaces of opposite charge becomes more stable than a neutral unique phase. This will be exemplified in particular on both the water/Pd and the complex water/Ru surface. We will show the method can be extended to finite temperature et allows predicting complex (nano)-structuration, thermic effects and even help to explain complex isotopic effects. Finally we will discuss the new developments in our group to obtaining the full electro-kinetic of a surface as a function of the potential or accounting for the solvent effects.

Fukui Function of a water/Pd(111) interface

1. J.-S. Filhol, M. Neurock, Angew. Chem. Int. Ed., 45 (2006) 402.
2. M. Mamatkulov, J.-S. Filhol, Phys. Chem. Chem. Phys.,13 (2011) 7675 – 7684
3. J.-S. Filhol, M.-L. Doublet, Catal. Today202 (2013) 87-97
4. M. Mamatkulov, J.-S. Filhol J. Phys. Chem. C 117 (2013) 2334-2343