Recent Advances in Real-Time Time-Dependent Density Functional Theory Simulations of Plasmonic Nanostructures and Plasmonic Photocatalysis

Abstract

Plasmonic catalysis provides a possible means for driving chemical reactions under relatively mild conditions. Rational design of these systems is impeded by the difficulty in understanding the electron dynamics and their interplay with reactions. Real-time, time-dependent density functional theory (RT-TDDFT) can provide dynamic information on excited states in plasmonic systems, including those relevant to plasmonic catalysis, at time scales and length scales that are otherwise out of reach of many experimental techniques. Here, we discuss previous RT-TDDFT studies of plasmonic systems, focusing on recent work that gains insight into plasmonic catalysis. These studies provide insight into plasmon dynamics, including size effects and the role of specific electronic states. Further, these studies provide significant insight into mechanisms underlying plasmonic catalysis, showing the importance of charge transfer between metal and adsorbate states, as well as local field enhancement, in different systems.

Bond Selective Photochemistry at Metal Nanoparticle Surfaces: CO Desorption from Pt and Pd

“…However, there may also be differences in the rate that CO on Pt and Pd dissipates the deposited vibrational energy from photoexcitation. To analyze differences in energy dissipation, real-time time-dependent density functional theory (RT-TD-DFT) , calculations were performed for CO adsorbed at the linear site and bridge site, respectively, of the (111) facet of 79-atom Pt and Pd nanoparticles (Figure S19). These simulations propagate the system in real time, giving dynamic information about the response to the excitation at time and length scales that are challenging to probe experimentally.…”

Plasmon-induced hot carrier distribution in a composite nanosystem: role of the adsorption site

“…In recent years, significant progress has been made in theoretical investigations employing real-time time-dependent density functional theory (rt-TDDFT) 50–57 simulations to gain insights into the generation and distribution of HCs. 30,33,58,59 In a previous rt-TDDFT investigation, 60 H 2 dissociation on linear Ag chains (up to n = 12) revealed the delocalization of charge density over time on both H 2 and Ag chains. Additionally, in another rt-TDDFT study, 61 using Ag and Au nanoparticles with 19, 55, and 225 atoms, dissociation of O 2 and N 2 at variable heights above the nanoparticles was observed.…”

Plasmonic‐assisted Electrocatalysis for CO2 Reduction Reaction

“…Identifying the dominant mechanism or their synergistic contribution to the plasmonic-assisted processes is an important issue in designing plasmonic electrocatalysts rationally. [60] Theoretical calculations are instrumental in uncovering the mechanisms of plasmonicassisted chemical reactions.…”

“…[61] TDDFT is one such model that enables the analysis of orbital interactions, energetic electron transfer, and the PES of excited and ground reaction pathways. [60] TDDFT calculations are utilized to investigate the absorption properties of metal clusters and structures with periodic boundary conditions. [62][63][64] Complementing this, real-time TDDFT (RT-TDDFT) provides deeper insights into dynamic processes related to excited states, which is particularly useful for studying plasmonic and other excitations in nanomaterials.…”

“…[62][63][64] Complementing this, real-time TDDFT (RT-TDDFT) provides deeper insights into dynamic processes related to excited states, which is particularly useful for studying plasmonic and other excitations in nanomaterials. [16,60]…”