The SAM model for wear inhibitor performance of dithiophosphates on iron oxide

Jiang S. Y., Frazier R., Yamaguchi E. S., Blanco M., Dasgupta S.,
Zhou Y. H., Cagin T., Tang Y. C., Goddard, III, W. A.,

J. Phys. Chem. B 101 7702-7709 (1997)


Zinc dithiophosphate (DTP) molecules have long been used as wear inhibitor oil additives for automotive engines. In order to obtain an atomistic understanding of the mechanism by which these molecules inhibit wear, we examined the geometries, energetics, and vibrations of an oxidized iron iron surface [(001) surface of alpha-Fe2O3] using the MSX force field (FF) based on ab initio quantum chemistry (QC) calculations, The DTP molecules studied include (RO)(2)PS2 with R = methyl, isobutyl, isopropyl, and phenyl. The alpha-Fe2O3 surface is described using the generalized valence bond (GVB) model of bonding. The geometries, binding energies, and vibrational frequencies from ab initio calculations on simple clusters are used with the biased Hessian method to develop the MSX FF suitable for describing the binding of DTP molecules to the surfaces. We find that the cohesive energies for the self-assembled monolayers (SAM) of the DTP molecules on the Fe2O3surface correlate with the antiwear performance observed in experimental engine tests. This suggests that the search for more effective and environmentally benign wear inhibitors can use the cohesive energies for SAM formation as a criterion in selecting and prioritizing compounds for experimental testing.