Utilizing plasmon-generated hot carriers to drive chemical reactions has currently become an active area of research in solar photocatalysis at the nanoscale. However, the mechanism underlying exact transfer and the...
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
Utilizing plasmon-generated hot carriers to drive chemical reactions has currently become an active area of research in solar photocatalysis at the nanoscale. However, the mechanism underlying exact transfer and the generation dynamics of hot carriers, and the strategies used to further improve the quantum efficiency of the photocatalytic reaction still deserve a further look. In this work, we perform a nonadiabatic excited-state dynamics study to depict the correlation between the reaction rate of plasmon-driven water splitting (PDWS) and the sizes of gold particles, the incident light frequency and intensity, and the near-field's spatial distribution. Four model systems, \ce{H2O} and \ce{Au20}@\ce{H2O} separately interacting with the laser field and the near field generated by the Au nanoparticle (NP) with a few nanometers in size, have been investigated. Our simulated results clearly unveil the mechanism of PDWS and hot-electron injection in a Schottky-free junction: the electrons populated on the antibonding orbitals of \ce{H2O} are mandatory to drive the \ce{OH} bond breaking and the strong orbital hybridization between \ce{Au20} and \ce{H2O} creates the condition for direct electron injection. We further find that the linear dependence of the reaction rate and the field amplitude only holds at a relatively weak field and it breaks down when the second {\ce{OH}} bond begins to dissociate and field-induced water fragmenting at a very intensive field, and that with the guarantee of electron injection, the water splitting rate increases with the increase of NP's size. This study will be helpful for further improving the efficiency of the photochemical reactions involving the plasmon-generated hot carriers and expanding the applications of hot carriers in varieties of chemical reactions.
Utilizing plasmon-generated hot carriers to drive chemical reactions has currently become an active area of research in solar photocatalysis at the nanoscale. However, the mechanism underlying exact transfer and the generation dynamics of hot carriers, and the strategies used to further improve the quantum efficiency of the photocatalytic reaction still deserve a further look. In this work, we perform a nonadiabatic excited-state dynamics study to depict the correlation between the reaction rate of plasmon-driven water splitting (PDWS) and the sizes of gold particles, the incident light frequency and intensity, and the near-field's spatial distribution. Four model systems, \ce{H2O} and \ce{Au20}@\ce{H2O} separately interacting with the laser field and the near field generated by the Au nanoparticle (NP) with a few nanometers in size, have been investigated. Our simulated results clearly unveil the mechanism of PDWS and hot-electron injection in a Schottky-free junction: the electrons populated on the antibonding orbitals of \ce{H2O} are mandatory to drive the \ce{OH} bond breaking and the strong orbital hybridization between \ce{Au20} and \ce{H2O} creates the condition for direct electron injection. We further find that the linear dependence of the reaction rate and the field amplitude only holds at a relatively weak field and it breaks down when the second {\ce{OH}} bond begins to dissociate and field-induced water fragmenting at a very intensive field, and that with the guarantee of electron injection, the water splitting rate increases with the increase of NP's size. This study will be helpful for further improving the efficiency of the photochemical reactions involving the plasmon-generated hot carriers and expanding the applications of hot carriers in varieties of chemical reactions.
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