The paradox of thermal vs. non-thermal effects in plasmonic photocatalysis

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Сен. 12, 2024

The debate surrounding the roles of thermal and non-thermal pathways in plasmonic catalysis has captured attention researchers sparked vibrant discussions within scientific community. In this review, we embark on a thorough exploration intriguing discourse, starting from fundamental principles culminating detailed understanding divergent viewpoints. We probe into core by elucidating behavior excited charge carriers illuminated nanostructures, which serves as foundation for two opposing schools thought. present key arguments evidence put forth proponents both pathways, providing perspective their respective positions. Beyond theoretical divide, discussed evolving methodologies used to unravel these mechanisms. discuss use Arrhenius equations variations, shedding light ensuing debates about applicability. Our review emphasizes significance localized surface plasmon resonance (LSPR), investigating its role collective oscillations decay dynamics that influence catalytic processes. also talked nuances activation energy, exploring relationship with nonlinearity temperature intensity dependence reaction rates. Additionally, address intricacies catalyst measurements implications light-triggered dynamics. further discusses wavelength-dependent rates, kinetic isotope effects, competitive electron transfer reactions, offering an all-inclusive view field. This not only maps current landscape photocatalysis but facilitates future explorations innovations unlock full potential plasmon-mediated catalysis, where synergistic approaches could lead different vistas chemical transformations.

Язык: Английский

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Plasmon Induced Charge Transfer Dynamics in Metallic Nanoparticle‐MoSe₂ Nanoflake Heterostructures

Advanced Optical Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 13, 2025

Abstract Plasmon‐induced hot carrier dynamics are crucial in various practical applications such as water splitting and photovoltaics. A hybrid system formed by interfacing plasmonic Au or Ag metal nanoparticles with triangular MoSe 2 nanoflakes is proposed, which also possess edge‐localized plasmons. Using time‐dependent density functional theory‐based simulations, this bi‐plasmonic shown to exhibit interfacial charge transfer induced excitations of either component. Tracking the fate photoinduced plasmons reveals that a significant pathway their decay involves direct hot‐carriers across interface. This study finds while likelihoods both hot‐electron hot‐hole transfers comparable, most cases considered, latter dominates. The extent net direction found depend on tunable features interface, including plasmon mode (nanoparticle nanoflake) excited polarization light used. It anticipated platform could prove extremely useful for widening substrate scope photocatalysis photodetection applications.

Язык: Английский

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Nuclear–Electronic Orbital Time-Dependent Configuration Interaction Method

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(23), С. 6017 - 6023

Опубликована: Май 30, 2024

Combining real-time electronic structure with the nuclear-electronic orbital (NEO) method has enabled simulation of complex nonadiabatic chemical processes. However, accurate descriptions hydrogen tunneling and double excitations require multiconfigurational treatments. Herein, we develop implement NEO time-dependent configuration interaction (NEO-TDCI) approach. Comparison to NEO-full CI calculations absorption spectra for a molecular system shows that NEO-TDCI approach can accurately capture splitting associated ground state as well vibronic progressions corresponding electron-proton excited states. Both these features are absent from obtained single reference methods. Our simulations dynamics illustrate oscillation proton density one side other via delocalized, bilobal wave function. These results indicate is highly suitable studying inherently systems.

Язык: Английский

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Effects of Nanowire Doping on Plasmon-Enhanced N₂ Dissociation

The Journal of Physical Chemistry A, Год журнала: 2024, Номер 128(19), С. 3784 - 3793

Опубликована: Май 4, 2024

Doping a transition metal element into plasmonic systems can tune the optical properties of system, which will potentially facilitate plasmon-enhanced catalytic process. In this study, we applied linear-response time-dependent density functional theory (LR-TDDFT) method with real-time electron dynamics and mean-field Ehrenfest methods to computationally investigate effects doping silver nanowires on N2 dissociation. We calculated absorption spectra for different doped systems, an external electric field performed examine how excitation affect activation or addition, also studied dopant affects system's electronic structure potential energy surface.

Язык: Английский

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Time-resolved vibronic spectra with nuclear–electronic orbital time-dependent configuration interaction

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(4)

Опубликована: Янв. 28, 2025

Time-resolved spectroscopy is an important tool for probing photochemically induced nonequilibrium dynamics and energy transfer. Herein, a method developed the ab initio simulation of vibronic spectra dynamical processes. This framework utilizes recently nuclear–electronic orbital time-dependent configuration interaction (NEO-TDCI) approach, which treats all electrons specified nuclei quantum mechanically on same footing. A strategy presented calculating time-resolved vibrational electronic absorption from any initial condition. Although this general TDCI implementation, utilizing NEO allows explicit inclusion quantized nuclei, as illustrated through calculation vibrationally hot spectra. produced by either or Rabi oscillations capture ground-state absorption, stimulated emission, excited-state between states. methodology provides foundation fully simulations multidimensional spectroscopic experiments.

Язык: Английский

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Energy conservation in real-time nuclear–electronic orbital Ehrenfest dynamics

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(14)

Опубликована: Апрель 8, 2025

Real-time nuclear–electronic orbital Ehrenfest (RT-NEO-Ehrenfest) dynamics methods provide a first-principles approach for describing nonadiabatic molecular processes with nuclear quantum effects. For an efficient description of proton transfer within RT-NEO-Ehrenfest dynamics, the basis function center associated can be allowed to move classically. This traveling (TPB) effectively captures although its energy conservation behavior is not yet fully satisfactory. Two recently proposed TPB approaches, in principle, conserve extended energy, which includes both system and kinetic center. Herein, thermostatted improve excluding In this approach, are modulated by dynamically rescaling momentum operator maintain conservation. With excited-state intramolecular o-hydroxybenzaldehyde as example, shown significantly while preserving accuracy achieved original approach.

Язык: Английский

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Density Functional Tight-Binding Captures Plasmon-Driven H₂ Dissociation on Al Nanocrystals

The Journal of Physical Chemistry C, Год журнала: 2025, Номер unknown

Опубликована: Апрель 25, 2025

Язык: Английский

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Realizing Direct Hot-Electron Transfer from Metal Nanoparticles to Per- and Polyfluoroalkyl Substances

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 4536 - 4546

Опубликована: Апрель 30, 2025

Per- and polyfluoroalkyl substances (PFAS) are a group of forever synthetic chemicals. They widely utilized in industries household appliances because their remarkable stability distinctive oil- water-repellent properties. Despite broad applications, unfortunately, PFAS hazardous to all forms life, including humans. In recent years, the environmental persistence has raised significant interest degrading these substances. However, strong C-F bonds chemicals pose several challenges degradation. Plasmons noble metal nanoparticles (NPs) offer many exciting photocatalytic reactions. an atomistic understanding plasmon-driven processes remains elusive. this work, using real-time time-dependent density functional theory, we have studied formation plasmons, hot-carrier generation, subsequent direct transfer from NPs PFAS. Our simulations show that there is apparent hot-electron Moreover, Ehrenfest dynamics simulations, demonstrated transferred hot electrons can efficiently degrade without requiring any external thermal bath. Thus, our work provides picture plasmon-induced efficient degradation We strongly believe generates impetus utilize plasmonic mitigate

Язык: Английский

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Assisting a Type-II Heterojunction with the LSPR Effect for Realizing Photocatalytic Hydrogen Peroxide Evolution with NIR Apparent Quantum Efficiency Exceeding 0.5%

Nano Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 21, 2025

Designing heterojunction catalysts for the production of hydrogen peroxide is a crucial strategy advancing field artificial photosynthesis. However, conventional type-II often face challenges weak redox ability and utilization charge carriers. Herein, distinct proposed that combines heterojunctions with localized surface plasmon resonance (LSPR) effect, thereby cooperatively enhancing high-energy electrons through hot electron injection process. The optimized catalyst MoO3-x-ZnIn2S4 (VMZS) exhibits H2O2 (47.2 μmol g-1 min-1) under simulated sunlight (AM1.5G, 100 mW cm-2) filter (λ > 350 nm) an apparent quantum efficiency 0.5% at 940 nm, significantly exceeding previously reported state-of-the-art catalysts. Moreover, prepared film VMZS enables rate 338.1 μM h-1. This work provides new insight on designing systems synergistic contribution carrier transfer route LSPR effect.

Язык: Английский

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Squeezed Protons and Infrared Plasmonic Resonance Energy Transfer

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(3), С. 751 - 757

Опубликована: Янв. 16, 2024

Unusual nuclear quantum effects may emerge near noble metal nanostructures such as squeezed vibrational states in molecular junctions and plasmonic resonance energy transfer the infrared domain. Herein, heavy metals are studied by nuclear–electronic orbital density functional theory (NEO-DFT) with an effective core potential. For a proton sandwiched between pair of gold tips modeled two Au6 clusters, NEO-DFT calculations suggest that can be tip distance decreases. HF molecule placed one-dimensional Au nanowire composed up to 34 atoms, real-time NEO time-dependent (RT-NEO-TDDFT) shows motion within resonantly electronic stretch mode. Overall, these illustrate advantages approach for probing effects, transfer.

Язык: Английский

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