Electronic Structure and Nonadiabatic Dynamics of Atomic Silver Nanowire-N₂Systems

Plasmonic nanoparticles can facilitate bond breaking and drive reactions of nearby molecules. Some of these processes involve bond activations which are traditionally challenging to accomplish. However, there is uncertainty in our understanding of the mechanisms through which plasmonic nanoparticles activate bonds and exactly how the plasmon resonance facilitates the bond breakage. Herein, we evaluate AgnN2 (n = 4, 6, 8) model systems via real-time time-dependent density functional theory (RT-TDDFT), linear response time-dependent density functional theory (LR-TDDFT), and Ehrenfest dynamics with a long-range corrected functional in order to better understand the charge-transfer process between the Ag system and the adsorbed small molecule. We find that charge-transfer states exist between Agn ς orbitals and antibonding orbitals of N2. Ehrenfest dynamics calculations reveal symmetry- and electric-field-dependent activation of N2 when coupled to the wire. This study serves as a step toward understanding the time-dependent electron and electron-nuclear dynamics that arise due to the interactions between plasmonic nanowires and small molecules.