The ONIOM method has become a succesful multilayer approach in the domain of homogeneous catalysis, and has been also applied in biochemical contexts. However, its application on surface interactions in the frontier between chemistry and material science has been more subdued.<br/><br/>In this presentation we report our work on the analysis of the bonding between an inorganic oligomer and a graphitic surface. It has been experimentally shown that a linear inorganic polymer composed by fifteen ruthenium units is able to absorb strongly on multiwalled carbon natotubes, and the resulting hybrid material is a powerful electroanode for water oxidation. Experimental techniques are however unable to characterize conclusively the interaction between the oligomer and the surface.<br/><br/>The reduced model used in our calculations involves nearly 3,000 atoms, with ten of them being ruthenium centers, and it becomes very challenging for a pure DFT calculation. Luckily, we were able to carry out a three-layer ONIOM(B97D:MM3:UFF) calculation. The resulting optimized geometry fits well with all experimental observations, and provides a rationale for the remarkable chemical properties of the system. The presentation will discuss the details of this structure, as well as the subtleties of the set-up of the ONIOM calculation using our Garleek series of scripts.

QM/MM/MM treatment with ONIOM for the interaction between a polymer and a surface

ACS Spring 2022

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