Multiscale modeling and simulation of surface‐enhanced spectroscopy and plasmonic photocatalysis

Abstract

Plasmonic metal nanoparticles (PMNPs) are capable of localized surface plasmon resonance (LSPR) and have become an important component in many experimental settings, such as the surface‐enhanced spectroscopy and plasmonic photocatalysts, in which PMNPs are used to regulate the nearby molecular photophysical and photochemical behaviors by means of the complex interplay between the plasmon and molecular quantum transitions. Building computational models of these coupled plasmon‐molecule systems can help us better understand the bound molecular properties and reactivity, and make better decisions to design and control such systems. Ab initio modeling the nanosystem remains highly challenging. Many hybrid quantum‐classical (or ‐quantum) computing models have thus been developed to model the coupled systems, in which the molecular system of interest is designated as the quantum mechanical (QM) sub‐region and treated by the excited‐state electronic structure approaches such as the time‐dependent density functional theory (TDDFT), while the electromagnetic response of PMNPs is usually described using either a computational/classical electrodynamic (CED) model, polarizable continuum model(PCM), a polarizable molecular mechanics (MM) force field, or a collective of optical oscillators in QED model, leading to many hybrid approaches, such as QM/CED, QM/PCM, QM/MM or ab initio QED. In this review, we summarize recent advances in the development of these hybrid models as well as their advantages and limitations, with a specific emphasis on the TDDFT‐based approaches. Some numerical simulations on the plasmon‐enhanced absorption and Raman spectroscopy, plasmon‐driven water splitting reaction and interfacial electronic injection dynamics in dye‐sensitized solar cell are demonstrated.This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Theoretical and Physical Chemistry > Spectroscopy Software > Quantum Chemistry Electronic Structure Theory > Combined QM/MM Methods

Time-Dependent Kohn-Sham Electron Dynamics Coupled with Nonequilibrium Plasmonic Response via Atomistic Electromagnetic Model

“…Ab initio modeling of the light-PMNP-molecule system remains highly challenging. Many hybrid quantum mechanics/classical mechanics or electrodynamics approaches have thus been developed to model the coupled systems, in which the molecule is described quantum-mechanically by the excited-state electronic structure approaches such as the time-dependent density functional theory (TDDFT), while the response of PMNPs are treated by classical electrodynamics methods, 13 such as Mie theory, 14 discrete dipole approximation (DDA), 15 finite difference time domain (FDTD), 16,17 and boundary element method (BEM). 18,19 However the continuum-dielectric assumption to MNPs becomes less apa) Electronic mail: liangwz@xmu.edu.cn propriate for medium to small-sized particles, in which the effects of size, shape, and edge on the plasmonic response cannot be ignored.…”

Real-Time Simulation of Ultrafast Electronic Dynamics of Nanoscale Systems Involving an Organic Molecule and a Nanoparticle Dimer

“…Elucidating the complex mechanisms usually requires a computational modeling and simulation of coupled systems. 10 Although plasmon−molecule systems have been intensively investigated experimentally and theoretically, the construction of a theoretical framework that can produce all of the disparate experimental observations is still in progress. Here we thus perform a simulation on the "real-time" electronic dynamics of a coupled molecule−plasmon nanoscale system by our newly developed multiscale approach, which combines the real-time time-dependent density functional theory (RT-TDDFT) approach with the time-domain frequency-dependent fluctuating charge (TD-ωFQ) model.…”

“…Furthermore, incomplete experimental information and complex dynamic interplay make the microscopic understanding challenging. Elucidating the complex mechanisms usually requires a computational modeling and simulation of coupled systems . Although plasmon–molecule systems have been intensively investigated experimentally and theoretically, the construction of a theoretical framework that can produce all of the disparate experimental observations is still in progress.…”