<br/>We have developed a polarizable frozen-density embedding (FDE) method for describing molecules adsorbed on metal clusters. The FDE method incorporates external orthogonality (EO) through the use of a level-shift projection operator to avoid the non-additive kinetic energy functional (KEDF). This is essential as current KEDFs tend to fail drastically for strongly overlapping systems. However, the FDE-EO method is computational very expensive due to freeze-and-thaw cycles needed for the method to reproduce the super-molecular DFT results. However, FDE-EO constitutes an exact embedding method at the DFT level of theory and thus can be used to benchmark the quality of approximate embedding methods. We have found that the expensive freeze-and-thaw cycles needed in the FDE-EO method can largely be eliminated through polarization embedding. The method is found to reproduce the ground-state density and dipole moment of small molecules interacting with metal clusters. For these systems there is significant charge-transfer between the molecule and the surface and thus represents a challenge for embedding methods.

Polarizable frozen density emdedding method for molecules on metal clusters

2019 Spring National Meeting

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