Theory of hot electrons: general discussion

Aizpurua, Javier; Baletto, Francesca; Baumberg, Jeremy J.; Christopher, Phillip; Nijs, Bart de; Deshpande, Preeti; Fernandez, Yuri Diaz; Fabris, Laura; Gawinkowski, Sylwester; Govorov, Alexander; Halas, Naomi J.; Hernandez, Romain; Jankiewicz, Bartłomiej J.; Khurgin, Jacob B.; Kuisma, Mikael; Kumar, Priyank V.; Lischner, Johannes; Liu, Jie; Marini, Andrea; Maurer, Reinhard J.; Mueller, Niclas S.; Parente, Matteo; Park, Jeong Young; Reich, Stéphanie; Sivan, Yonatan; Tagliabue, Giulia; Torrente‐Murciano, Laura; Thangamuthu, Madasamy; Xu, Xiaofei; Zayats, Anatoly

doi:10.1039/c9fd90012h

Cited by 40 publications

(42 citation statements)

References 6 publications

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“…47 The oscillatory population and depopulation of these states indicate that they would not likely be individually separable while they are a part of the plasmon as Coulomb interaction is an essential part of the excitation. 48 The resonant transitions have zero Coulomb energy contribution and the occupations of the corresponding electron and hole states grow steadily as the plasmon decays (Fig. 2c; solid lines).…”

Section: Resultsmentioning

confidence: 93%

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Hot-Carrier Generation in Plasmonic Nanoparticles: The Importance of Atomic Structure

2020

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Metal nanoparticles are attractive for plasmon-enhanced generation of hot carriers, which may be harnessed in photochemical reactions. In this work, we analyze the coherent femtosecond dynamics of photon absorption, plasmon formation, and subsequent hot-carrier generation through plasmon dephasing using first-principles simulations. We predict the energetic and spatial hot-carrier distributions in small metal nanoparticles and show that the distribution of hot electrons is very sensitive to the local structure. Our results show that surface sites exhibit enhanced hot-electron generation in comparison to the bulk of the nanoparticle. Although the details of the distribution depend on particle size and shape, as a general trend, lower-coordinated surface sites such as corners, edges, and {100} facets exhibit a higher proportion of hot electrons than higher-coordinated surface sites such as {111} facets or the core sites. The present results thereby demonstrate how hot carriers could be tailored by careful design of atomic-scale structures in nanoscale systems.

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Section: Resultsmentioning

confidence: 93%

“… 49 The oscillatory population and depopulation of these states indicate that they would not likely be individually separable while they are a part of the plasmon as the Coulomb interaction is an essential part of the excitation itself. 50 …”

Section: Resultsmentioning

confidence: 99%

Hot-Carrier Generation in Plasmonic Nanoparticles: The Importance of Atomic Structure

2020

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“…In direct and hybrid plasmonic photocatalysis, it is important to distinguish between electron‐ and heat‐driven photochemistry. [ 118,192–196 ] Christopher et al. have proposed that the trend of the photocatalytic rate as a function of incident light intensity and kinetic isotopic effects (KIEs) can be used to make this distinction.…”

Section: Lspr‐mediated Pathways Responsible For Photocatalytic Enhancement On Hpnsmentioning

confidence: 99%

Photoinduced Electron and Energy Transfer Pathways and Photocatalytic Mechanisms in Hybrid Plasmonic Photocatalysis

Ramakrishnan

Mohammadparast

Dadgar

et al. 2021

Advanced Optical Materials

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Hybrid plasmonic nanostructures are built on plasmonic metalnanostructures surrounded by catalytic metals or metal oxides. Recent studies have shown that hybrid plasmonic nanocatalysts can concurrently utilize thermal energy and photon stimuli and exhibit high catalytic activity, selectivity, and stability that are not attainable in conventional purely thermally activated catalytic processes. The hybrid plasmonic photocatalytic approach has recently emerged as an attractive concept for the conversion of solar energy into chemical energy, the distributed synthesis of valuable chemicals such as ammonia with little to no requirement of external heating, and the development of coke‐resistant and selective catalytic processes. The field of hybrid plasmonic photocatalysis has grown tremendously in the last decade. In this review article, the advantages of visible‐light‐augmented hybrid plasmonic photocatalysis over conventional pure thermally activated heterogeneous catalysis are discussed. Fundamental insights are provided into photocatalytic mechanisms by which the photoexcited charge carriers (electrons and holes) are formed and transferred to adsorbates triggering chemical transformations on the surface of hybrid plasmonic nanocatalysts. Computational modeling used for predicting and understanding the photocatalytic activity and selectivity on hybrid plasmonic nanostructures is also reviewed. The review closes with a discussion of the current challenges, new opportunities, and future outlook for hybrid plasmonic photocatalysis.

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“…As extensively discussed in the literature, an accurate description of the optical phenomena occurring in plasmonic nanostructures requires the electron excitation to be dealt with from different perspectives, [ 22–25 ] such as the quasi‐classical description [ 26 ] (including the Drude model and the kinetic Boltzmann approach) and the quantum formalism. [ 27 ] In particular, quantum effects have to be accounted for when describing the generation of high‐energy nonthermal electrons.…”

Section: Introductionmentioning

confidence: 99%

“…quickly collide and exchange their energies with many lowerenergy electrons (electron thermalization) producing a thermalized electron distribution characterized by an overall increased electron temperature. [19][20][21] As extensively discussed in the literature, an accurate description of the optical phenomena occurring in plasmonic nanostructures requires the electron excitation to be dealt with from different perspectives, [22][23][24][25] such as the quasi-classical description [26] (including the Drude model and the kinetic Boltzmann approach) and the quantum formalism. [27] In particular, quantum effects have to be accounted for when describing the generation of high-energy nonthermal electrons.…”

Section: Introductionmentioning

confidence: 99%

Disentangling the Temporal Dynamics of Nonthermal Electrons in Photoexcited Gold Nanostructures

O’Keeffe

Catone

Mario

et al. 2021

Laser & Photonics Reviews

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The study of nonthermal electrons, generated upon photoexcitation of plasmonic nanostructures, plays a key role in a variety of contexts, from photocatalysis and energy conversion to photodetection and nonlinear optics. Their ultrafast relaxation and subsequent release of energy to a low energy distribution of thermalized hot electrons has been the subject of a myriad of papers, mostly based on femtosecond transient absorption spectroscopy (FTAS). However, the FTAS signal stems from a complex interplay of different contributions arising from both nonthermal and thermal electrons, making the disentanglement of the two a very challenging task, so far accomplished only in terms of numerical simulations. Here a combined approach is introduced, based on a post-processing of the FTAS measurements guided by a reduced semiclassical model, the so-called extended two-temperature model, which has allowed the purely nonthermal contribution to the pump-probe experimental map recorded for 2D arrays of gold nanoellipsoids to be isolated. This approach displays the intimate correlation between electron energy and probe photon energy on the ultrafast time-scale of electron thermalization. It also sheds new light on the ultrafast transient optical response of gold nanostructures, and will help the development of optimized plasmonic configurations for nonthermal electrons generation and harvesting.

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Theory of hot electrons: general discussion

Cited by 40 publications

References 6 publications

Hot-Carrier Generation in Plasmonic Nanoparticles: The Importance of Atomic Structure

Hot-Carrier Generation in Plasmonic Nanoparticles: The Importance of Atomic Structure

Photoinduced Electron and Energy Transfer Pathways and Photocatalytic Mechanisms in Hybrid Plasmonic Photocatalysis

Disentangling the Temporal Dynamics of Nonthermal Electrons in Photoexcited Gold Nanostructures

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