Plasmon-induced excited-state catalysis understood via embedded correlated wavefunction theory
Invited
Abstract
Metallic nanoparticles (MNPs) with nearly-free-electron-like valence electrons have enhanced ability to scatter/absorb light by means of local surface plasmon resonances (LSPRs). Such LSPRs produce amplified electric fields that can excite molecules or other materials coupled to the MNPs. Photocatalysis mediated by MNPs exploits this unique optical phenomenon. First-principles quantum mechanics can aid in understanding such light-driven chemistry but the methods used must properly account for both electronic excitations and surface reactions. Embedded correlated wavefunction (ECW) theory is ideally suited for this purpose, wherein the extended surface is described by an embedding potential derived from density functional embedding theory (DFET). The chemical reaction then is treated with CW theory subject to this DFET-derived potential. ECW calculations of a variety of endoergic reactions on pure and doped surface-plasmon-active metals reveal that enhanced kinetics can occur on excited-state reactive potential energy surfaces accessed via plasmon-enhanced light absorption or resonance energy transfer. Our calculations explain experimentally observed plasmon-driven enhanced rates and suggest candidate MNPs for photocatalytic nanoplasmonics.
–
Presenters
-
Emily Carter
Office of the Chancellor, University of California Los Angeles, University of California, Los Angeles, UCLA, Office of Chancellor, University of California Los Angeles, Office of the Chancellor, University of California, Los Angeles
Authors
-
John Mark P. Martirez
Department of Chemical and Biomolecular Engineering, University of California, Los Angeles
-
Junwei L. Bao
Department of Mechanical and Aerospace Engineering, Princeton University
-
Emily Carter
Office of the Chancellor, University of California Los Angeles, University of California, Los Angeles, UCLA, Office of Chancellor, University of California Los Angeles, Office of the Chancellor, University of California, Los Angeles