Electronic Structure and Nonadiabatic Dynamics of Atomic Silver Nanowire–N₂ Systems

Abstract

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 Ag n N 2 (n = 4, 6, 8) model systems via real-time time-dependent density functional theory (RT-TDDFT), linear response timedependent 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 Ag n Σ orbitals and antibonding orbitals of N 2 . Ehrenfest dynamics calculations reveal symmetry-and electric-fielddependent activation of N 2 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.

Dynamical evolution of the Schottky barrier as a determinant contribution to electron–hole pair stabilization and photocatalysis of plasmon-induced hot carriers

“…Hot carrier injection from a metallic cluster to semiconductors has been studied by nonadiabatic molecular dynamics, 38,39 and recently a detailed description of the charge localization in an Ag-TiO 2 hybrid system has been performed by means of real-time time-dependent DFT (RT-TD-DFT). 40 Besides, nonadiabatic molecular dynamics has been employed to study the dissociation of H 2 on gold NP dimers, 41 N 2 dissociation by hot carriers produced in silver wireste 42 and water splitting over gold NP. 43 In this context, by means of real-time time-dependent tight-binding DFT (RT-TD-DFTB) electronic and electron-ion dynamics, we studied the hot carrier injection in the paradigmatic Au-TiO 2 system.…”

Dynamical evolution of the Schottky barrier as a determinant contribution to electron-hole pair stabilization and photocatalysis of plasmon-induced hot carriers

“…Hot carrier injection from a metallic cluster to semiconductors have been studied by nonadiabatic molecular dynamics, 38,39 and recently a detailed description of the charge localization in a Ag-TiO 2 hybrid system has been performed by means of real-time time-dependent DFT (RT-TD-DFT). 40 Besides, nonadiabatic molecular dynamics has been employed to study the dissociation of H 2 on gold NPs dimers, 41 N 2 dissociation by hot carriers produced in silver wires 42 and water splitting over gold NP. 43 In this context, by means of real-time time-dependent tight-binding DFT (RT-TD-DFTB) electronic and electron-ion dynamics, we studied the hot carrier injection in the paradigmatic Au-TiO 2 system.…”

Understanding the mechanism of plasmon-driven water splitting: hot electron injection and a near field enhancement effect

“…For direct electron transfer, 18,21 in the presence of empty hybridized orbitals due to the strong metal-adsorbate coupling, chemical interface damping 22,23 can induce the plasmon dephasing directly and generate nonthermalized electrons in the empty hybridized orbitals. The plasmon-induced hot carrier transfer has been utilized to foster various photochemistry processes, such as the dissociation of H 2 , 24-26 N 2 , 27 and O 2 , 28,29 CO 2 reduction, 15,30 water splitting [31][32][33] and organic transformations. 34 The solar photocatalytic water splitting is a promising method for hydrogen production.…”