The adsorption of acrolein on a Pt (111): A study of chemical bonding and electronic structure

SILVINA PIRILLO; IGNACIO LóPEZ-CORRAL; ESTEFANíA GERMáN; ALFREDO JUAN

APPLIED SURFACE SCIENCE

ELSEVIER SCIENCE BV

Lugar: Amsterdam; Año: 2012 vol. 263 p. 79 - 85

0169-4332

The adsorption of acrolein on a Pt (111) surface was studied using ab-initio and semiempirical calculations. Geometry optimization and densities of states (DOS) curves were carried out using the Vienna Ab-initio Simulation Package (VASP) code. We started our study with the preferential geometries corresponding to the different acrolein/Pt (111) adsorption modes previously reported. Then, we examined the evolution of the chemical bonding in these geometries, using the crystal orbital overlap populations (COOP) and overlap population (OP) analysis of selected pairs of atoms. We analyzed the acrolein intramolecular bonds, Pt (111) superficial bonds and new molecule-surface formed bonds after adsorption. We found that Pt-Pt bonds interacting with the molecule and acrolein C=O and C=C bonds are weakened after adsorption; this last bond is significantly linked to the surface. The obtained C-Pt and O-Pt OP values suggest that the most stable adsorption modes are ç3-cis and ç4-trans, while the ç1-trans is the less favored configuration. We also found that C pz orbital and Pt pz and dz2 orbitals participate strongly in the adsorption process.