Plasmon-induced excited-state catalysis understood via embedded correlated wavefunction theory

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.