The adsorption of acrolein on a Pt (1 1 1) 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 (1 1 1) adsorption modes previously reported. Then, we examined the evolution of the chemical bonding in these geometries, using the crystal orbital overlap population (COOP) and overlap population (OP) analysis of selected pairs of atoms. We analyzed the acrolein intramolecular bonds, Pt (1 1 1) 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 eta(3)-cis and eta(4)-trans, while the eta(1)-trans is the less favored configuration. We also found that C pz orbital and Pt pz and d(z2) orbitals participate strongly in the adsorption process. (C) 2012 Elsevier B.V. All rights reserved.