Theoretical Investigations on the Plasmon-Mediated Dissociation of Small Molecules in the Presence of Silver Atomic Wires.

Plasmonic nanoparticles can promote bond activation in adsorbed molecules under relatively benign conditions via excitation of the nanoparticle's plasmon resonance. As the plasmon resonance often falls within the visible light region, plasmonic nanomaterials are a promising class of catalysts. However, the exact mechanisms through which plasmonic nanoparticles activate the bonds of nearby molecules are still unclear. Herein, we evaluate Ag 8 -X 2 (X = N, H) model systems via real-time time-dependent density functional theory (RT-TDDFT), linear response time-dependent density functional theory (LR-TDDFT), and Ehrenfest dynamics in order to better understand the bond activation processes of N 2 and H 2 facilitated by the presence of the atomic silver wire under excitation at the plasmon resonance energies. We find that dissociation is possible for both small molecules at high electric field strength. Activation of each adsorbate is symmetry- and electric field-dependent, and H 2 activates at lower electric field strengths than N 2 . This work serves as a step toward understanding the complex time-dependent electron and electron-nuclear dynamics between plasmonic nanowires and adsorbed small molecules.