(281f) First Principles Modeling of Plasmon-Mediated Charge Transfer Mechanisms for Photo-Catalytic Rate Enhancement

We have recently reported that optically excited plasmonic nano-particles can activate photo-chemical transformations.[1,2] These

reactions exhibit a number of unique characteristics compared to other photo-catalysts and catalytic reactions. In this contribution we

have used quantum chemical ab-initio approaches to model plasmon-mediated photo-chemical reactions on metals.[3–4] A number of

different mechanisms for the hot electron-driven activation of adsorbates on plasmonic metal surfaces will be discussed and analyzed in

the context of experimental results. I will discuss how the electronic structure can drive optical properties and effect chemical

transformations of adsorbates.

REFERENCES

[1]      P. Christopher, H. Xin, A. Marimuthu, S. Linic, Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures., Nat. Mater. 11 (2012) 1044–50.

[2]      S. Linic, P. Christopher, D.B. Ingram, Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy., Nat. Mater. 10 (2011) 911–921.

[3]      L. Genzel, T.P. Martin, U. Kreibig, Dielectric function and plasma resonances of small metal particles, Zeitschrift Für Phys. B Condens. Matter Quanta. 21 (1975) 339–346.

[4]      T. Olsen, J. Schiotz, Origin of Power Laws for Reactions at Metal Surfaces Mediated by Hot Electrons. 23 (2009) 238301.