Abstract: Rhodium (Rh) nanoparticles have attracted a lot of attention due to their strong and ambient-stable UV plasmonic response. Very recently, the synthesis of Rh tetrahedra with and without concave defect-rich surfaces serving in plasmon assisted photocatalytic energy conversion has been reported. In this work, we perform a systematic numerical study on plasmonic behavior and surface charge distribution in order to optimize the use of Rh tetrahedra in surface-enhanced spectroscopies and photocatalysis. We analyze the effect of the edges and corners reshaping, a deformation already reported to appear in Rh nanocubes which have been repeatedly re-used in photocatalytic processes. It is demonstrated that rounding the edges and corners weakens both the near-field enhancement and surface charge densities in these locations, which in turn are the more reactive regions due to the presence of uncoordinated sites. In addition, we study how the near-field and charge density is redistributed on the surface of the tetrahedra when concavities of different sizes and depths are introduced. Through this study, we show that, in order to simultaneously maximize the near-field enhancement and surface charge densities in the concavity and at external edges and corners, medium size deep concavities are needed.

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