387164 First Principles Modeling of Surface Plasmon Dynamics and Mechanism for Photo-Catalytic Rate Enhancement

Tuesday, November 18, 2014: 1:36 PM
307 (Hilton Atlanta)
Matthew Morabito1, Hongliang Xin2 and Suljo Linic1, (1)Department of Chemical Engineering, University of Michigan, Ann Arbor, MI, (2)Department of Chemical Engineering, Stanford University, Stanford, CA

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 fundamentally different than other photo-catalysts and catalytic reactions.  In this contribution we have used quantum chemical approaches to model the plasmon-driven photo-chemical reactions on metals.[3–6] I will discuss the time-dependent evolution of the electronic structure of optically excited plasmonic metals. Furthermore, I will show how this electronic structure interacts with adsorbates, ultimately driving chemical transformations of the adsorbates. A number of conflicting mechanisms will be discussed and analyzed in the context of previously reported experimental results. 

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) 911–21.

[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]      S. Monturet, P. Saalfrank, Role of electronic friction during the scattering of vibrationally excited nitric oxide molecules from Au(111), Phys. Rev. B. 82 (2010) 075404.

[5]      V. Krishna, J.C. Tully, Vibrational lifetimes of molecular adsorbates on metal surfaces., J. Chem. Phys. 125 (2006) 054706.

[6]      T. Olsen, J. Schiotz, Quantum corrected Langevin dynamics for adsorbates on metal surfaces interacting with hot electrons., J. Chem. Phys. 133 (2010) 034115.

[7]      S.I. Anisimov, B. Rethfeld, Theory of ultrashort laser pulse interaction with a metal, in: V.I. Konov, M.N. Libenson (Eds.), Nonreson. Laser-Matter Interact., International Society for Optics and Photonics, 1997: pp. 192–203.

[8]      Z. Lin, L. Zhigilei, V. Celli, Electron-phonon coupling and electron heat capacity of metals under conditions of strong electron-phonon nonequilibrium, Phys. Rev. B. 77 (2008) 075133.


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