Semi-empirical and ab initio quantum chemical characterisation of pyridine derivatives as HCl inhibitors of aluminium surface

Quantum chemical methods are becoming ever more prevalent for assessing surface interactions of different molecules using cluster models and semi-empirical, ab initio Hartree-Fock and density functional theory (DFT) studies considering the standard potential energy surfaces. Examination of the efficacy of some pyridine derivatives to counter aluminium corrosion in hydrochloric acid using ab initio and semi-empirical quantum chemical deductions and its comparison with the available experimental data forms the basis of this research. It is believed that the inhibition efficiency has lucid correlation with the total energy of inhibitor molecules and highest occupied molecular orbital energy levels calculated by DFT study methods and thus the adsorption energy for the pyridine on Al-1, Al-5, Al-14, Al-18 and Al-26 clusters are determined to assess the convergence of the results with respect to size of the cluster. Subsequently, Al-26 is used for the inhibitor/aluminium cluster interface investigations. Results highlight the reaction between pyridine molecules and appropriately active sites such as corners and steps or kinks and screw dislocations towards which pyridine molecules are attracted as is evident from a three times rise in adsorption energy from (-35) to (-107) kJ mol(-1). Therefore, inhibition mechanism is primarily associated with local properties. Interactions take place between the surface defect and the nitrogen group of the pyridine molecule however, the possibility of ion pair formation between protonated pyridine and chloride ion and its influence on the general adsorption of pyridine on aluminium is also examined. The interaction energies of pyridine and aluminium cluster with the natural bond orbital are also reported. (C) 2008 Elsevier B.V. All rights reserved.