Plasmon Relaxation Research Articles

Probing Spatial Energy Flow in Plasmonic Catalysts from Charge Excitation to Heating: Nonhomogeneous Energy Distribution as a Fundamental Feature of Plasmonic Chemistry.

Plasmonic catalysts use light to drive chemical reactions. One critical question is how light energy moves at nanoscales in these complex systems, leading to chemical transformations. In this contribution, we map out this energy flow by developing approaches to measure spatial temperature distributions in heterogeneous plasmonic catalysts, consisting of three-dimensional networks of plasmonic nanoparticles anchored on an oxide support. We survey the local temperatures of molecules adsorbed on catalytically active plasmonic nanoparticles, the nanoparticles themselves, and the catalyst support, under steady-state continuous-wave illumination. We reveal the existence of large temperature gradients, in which the local temperatures of the molecules, nanoparticles, and the surrounding environment can vary greatly. We show that these temperature gradients are a natural consequence of plasmon relaxation, involving the interconversion between electromagnetic light energy, electronic excitations, and heating of various entities as these electronic excitations relax. The presence of these gradients is a fundamental and unique feature of gas-phase plasmonic catalysis.

Optimal Geometry for Plasmonic Hot-Carrier Extraction in Metal-Semiconductor Nanocrystals.

Plasmon-induced energy and charge transfer from metal nanostructures hold great potential for harvesting solar energy. Presently, the efficiencies of charge-carrier extraction are still low due to the competitive ultrafast mechanisms of plasmon relaxation. Using single-particle electron energy loss spectroscopy, we correlate the geometrical and compositional details of individual nanostructures to their carrier extraction efficiencies. By removing ensemble effects, we are able to show a direct structure-function relationship that permits the rational design of the most efficient metal-semiconductor nanostructures for energy harvesting applications. In particular, by developing a hybrid system comprising Au nanorods with epitaxially grown CdSe tips, we are able to control and enhance charge extraction. We show that optimal structures can have efficiencies as high as 45%. The quality of the Au-CdSe interface and the dimensions of the Au rod and CdSe tip are shown to be critical for achieving these high efficiencies of chemical interface damping.

Investigation of plasmon relaxation mechanisms using nonadiabatic molecular dynamics.

Hot carriers generated from the decay of plasmon excitation can be harvested to drive a wide range of physical or chemical processes. However, their generation efficiency is limited by the concomitant phonon-induced relaxation processes by which the energy in excited carriers is transformed into heat. However, simulations of dynamics of nanoscale clusters are challenging due to the computational complexity involved. Here, we adopt our newly developed Trajectory Surface Hopping (TSH) nonadiabatic molecular dynamics algorithm to simulate plasmon relaxation in Au20 clusters, taking the atomistic details into account. The electronic properties are treated within the Linear Response Time-Dependent Tight-binding Density Functional Theory (LR-TDDFTB) framework. The relaxation of plasmon due to coupling to phonon modes in Au20 beyond the Born-Oppenheimer approximation is described by the TSH algorithm. The numerically efficient LR-TDDFTB method allows us to address a dense manifold of excited states to ensure the inclusion of plasmon excitation. Starting from the photoexcited plasmon states in Au20 cluster, we find that the time constant for relaxation from plasmon excited states to the lowest excited states is about 2.7ps, mainly resulting from a stepwise decay process caused by low-frequency phonons of the Au20 cluster. Furthermore, our simulations show that the lifetime of the phonon-induced plasmon dephasing process is ∼10.4fs and that such a swift process can be attributed to the strong nonadiabatic effect in small clusters. Our simulations demonstrate a detailed description of the dynamic processes in nanoclusters, including plasmon excitation, hot carrier generation from plasmon excitation dephasing, and the subsequent phonon-induced relaxation process.

Plasmon resonance of gold and silver nanoparticle arrays in the Kretschmann (attenuated total reflectance) vs. direct incidence configuration

While the behaviour of plasmonic solid thin films in the Kretschmann (also known as Attenuated Total Reflection, ATR) configuration is well-understood, the use of discrete nanoparticle arrays in this optical configuration is not thoroughly explored. It is important to do so, since close packed plasmonic nanoparticle arrays exhibit exceptionally strong light-matter interactions by plasmonic coupling. The present work elucidates the optical properties of plasmonic Au and Ag nanoparticle arrays in both the direct normal incidence and Kretschmann configuration by numerical models, that are validated experimentally. First, hexagonal close packed Au and Ag nanoparticle films/arrays are obtained by air–liquid interfacial assembly. The numerical models for the rigorous solution of the Maxwell’s equations are validated using experimental optical spectra of these films before systematically investigating various parameters. The individual far-field/near-field optical properties, as well as the plasmon relaxation mechanism of the nanoparticles, vary strongly as the packing density of the array increases. In the Kretschmann configuration, the evanescent fields arising from p- and s-polarized (or TM and TE polarized) incidence have different directional components. The local evanescent field intensity and direction depends on the polarization, angle of incidence and the wavelength of incidence. These factors in the Kretschmann configuration give rise to interesting far-field as well as near-field optical properties. Overall, it is shown that plasmonic nanoparticle arrays in the Kretschmann configuration facilitate strong broadband absorptance without transmission losses, and strong near-field enhancement. The results reported herein elucidate the optical properties of self-assembled nanoparticle films, pinpointing the ideal conditions under which the normal and the Kretschmann configuration can be exploited in multiple light-driven applications.

Disentangling plasmonic and catalytic effects in a practical plasmon-enhanced Lithium–Oxygen battery

Despite possessing high theoretical energy density, rechargeable Li–O2 batteries face critical drawbacks towards commercialization. In line with recent attempts to integrate solar energy exploitation in high-energy storage, here we investigate the promise of plasmonic materials with unique light-interacting properties (localized surface plasmon resonance, LSPR) and emerging application in catalysis. Au nanoparticles (NPs) at increasing contents/sizes are incorporated on conventional Ketjen Black cathodes, with preliminary half-cell measurements underlining the promise of LSPR-generated hot-carriers on the O2 electrochemistry. The illuminated battery with facile Li2O2 formation/decomposition, small Li2O2 particles, and suppressed carboxylate side-products unlocks a round-trip efficiency boost from 75.2 to 80.2% (first cycle) and a ∼1.2-fold full capacity enhancement. Even more remarkably, with continuous cycling (30 cycles), a 680 mV-overpotential suppression is here reported. Comparatively, dark conditions reveal negligible Au-driven catalytic effects, whereas LSPR-induced local heat effects are ruled out upon meticulous assessment of the product selectivity in cells at increasing temperatures. These outstanding efficiencies are ensured even with larger particles (5–100 nm), as corroborated by corresponding galvanostatic profiles and finite-difference time-domain simulations, pinpointing the practicality of our cathodes towards scale-up. This contribution is the first to disentangle catalytic effects and plasmon relaxation pathways over practical carbon-based cathodes for high-energy storage.

Plasmon Mediated Electron Transfer and Temperature Dependent Electron-Phonon Scattering in Gold Nanoparticles Embedded in Dielectric Films.

Excitation of localized surface plasmon resonance in metal nanoparticles (NPs) embedded in a glassy matrix generates hot electrons, which can be extracted for different optoelectronic applications. The insights of plasmon relaxation dynamics with varying surrounding dielectric environments and temperature dependence electron-phonon scattering process in gold (Au) NPs are still not very clear. Here, we have employed ultrafast transient absorption (TA) spectroscopy to explore the hot plasmon mediated electron transfer (PMET) and electron-phonon dynamics of photo-excited Au NPs in glassy film matrix with variable SiO2 /TiO2 compositions at cryogenic (5 K) to room temperature (300 K). Herein, we have chosen two pump excitation wavelengths (400 and 700 nm). The 400 nm excitation (d→sp) generates hot electron and the 700 nm excitation (sp→sp) provide information of direct plasmon relaxation. Drastic reduction of the transient signal of Au NPs in the high TiO2 content film as compared to pure SiO2 confirm hot electron transfer (HET) from Au plasmon to TiO2 . Electron-phonon scattering time constant (τe-ph ) of Au NPs in the glassy film is found to be faster in presence of TiO2 due to facile electron transfer/injection. Temperature dependent TA studies suggest that electron-phonon scattering time decreases with temperature. These findings would assist to develop more advanced photo-voltaic, opto-electronic and quantum optic-based devices using the plasmonic metal NPs.

Directional Damping of Plasmons at Metal-Semiconductor Interfaces.

ConspectusOver the past decade, it has been shown that surface plasmons can enhance photoelectric conversion in photovoltaics, photocatalysis, and other optoelectronic applications through their plasmonic absorption and damping processes. However, plasmonically enhanced devices have yet to routinely match or exceed the efficiencies of traditional semiconductor devices. The effect of plasmonic losses dissipates the absorbed photoenergy mostly into heat and that has hampered the realization of superior next-generation plasmonic optoelectronic devices. Several approaches are being explored to alleviate this situation, including using gain to compensate for the plasmonic losses, designing and synthesizing alternative low-loss plasmonic materials, and reducing activation barriers in plasmonic devices and physical thicknesses of photoabsorber layers to lower the plasmonic losses. A newly proposed plasmon-induced interfacial charge-transfer transition (PIICTT) mechanism has proven to be effective in minimizing energy loss during interfacial charge transfer. The PIICTT leads to a damping of metallic plasmonics by directly generating excitons at the plasmonic metal/semiconductor heteronanostructures. This novel concept has been proven to overcome some of the limitations of electron-transfer inefficiencies, renewing a focus on surface plasmon damping processes with the goal that the plasmonic excitation energies of metal nanoparticles can be more efficiently transferred to the adjacent semiconductor components in the absence and presence of an effective interlayer of carrier-selective blocking layer (CSBL). Several theoretical and experimental studies have concluded that efficient plasmon-induced ultrafast hot-carrier transfer was observed in plasmonic-metal/semiconductor heteronanostructures. The PIICTT mechanism may well be a general phenomenon at plasmonic metal/semiconductor, metal/molecule, semiconductor/semiconductor, and semiconductor/molecule heterointerfaces. Thus, the PIICTT presents a new opportunity to limit energy loss in plasmonic-metal nanostructures and increase device efficiencies based on plasmonic coupling. The nonradiative damping of surface plasmons can impact the energy flux direction and thereby provide a new process beyond light trapping, focusing, and hot carrier creation.In this Account, we draw much attention to the benefits of interfacial plasmonic coupling, highlighting recent pioneering discoveries in which plasmon-induced interfacial charge- and energy-transfer processes enable the generation of hot charge carriers near the plasmonic-metal/semiconductor interfaces. This process is likely to increase the photoelectric conversion efficiency, constituting "plasmonic enhancement". We also discuss recent advances in the dynamics of surface plasmon relaxation and highlight exciting new possibilities for plasmonic metals and their interactions with strongly attached semiconductors to provide directional energy fluxes. While this new research area comes on the heels of much elaborate research on both metal and semiconductor nanomaterials, it provides a subtle but important refinement in understanding the optoelectronic properties of materials with far-reaching consequences from fundamental interface science to technological applications. We hope that this Account will contribute to a more systematic description of interface-coupled plasmonics, both fundamentally and in terms of applications toward the design of plasmonic heterostructured devices.

Modulation of plasmonic relaxation damping by surface phonons

We experimentally study the effect of amplitude-varying surface acoustic waves on a localized surface plasmon (LSP), which unveils exceptional properties of plasmon-phonon interaction with promising applications in future tunable photonic devices. Gold nanoparticles are deposited on X-cut LiNbO 3 to generate plasmonic oscillation, and an interdigital transducer is fabricated to create surface acoustic wave pulses. The interaction between an amplitude-varying mechanical wave and a plasmonic oscillation affects different plasmon dynamics and relaxation gradients, leading to a systematic change in LSP absorption. We also demonstrated the effect of polarized light on the device, providing a unique characteristic to explore the manipulation process effectively.

Chemical Interface Damping in Nonstoichiometric Semiconductor Plasmonic Nanocrystals: An Effect of the Surrounding Environment.

Semiconductor plasmonic nanocrystals (NCs) have been utilized for an enormous number of plasmon-enhanced spectroscopic and energy conversion applications. Plasmonic NCs are extremely high light absorbers, and optical properties can be easily manipulated across the UV-vis-NIR spectrum region by changing mere chemical compositions and the surrounding environment of the NCs. This feature article focuses on reassessing plasmon dynamics by changing the interface composition between NCs and the surrounding medium to ascertain the damping contribution from chemical interface damping (CID). Also, this feature article deciphers a fundamental understanding of hot-carrier relaxation and extraction from plasmonic materials. On the route to determining the different relaxation dynamics of nonstoichiometric Cu2-xS/Se NCs, we have employed a transient ultrafast pump-probe broadband spectrometer. First, we have described the ultrafast plasmon relaxation dynamics of nonstoichiometric Cu2-xS NCs by varying the copper to sulfur ratio, and then we carefully compare how two surface ligands (oleylamine and 3-mercaptopropionic acid) lead to significantly different transient kinetics of the same plasmonic (Cu2-xSe) NCs because of different capping agents. Along with this, we have described the impact of a molecular adsorbate (methylene blue) on ultrafast plasmon relaxation dynamics of the nonstoichiometric Cu2-xSe NCs system. Finally, the chemical interface damping effect has been compared in the Cu2-xS NCs system after capping with two distinct capping ligands: oleylamine and oleic acid. For the proof of concept, plasmonic thin-film devices were fabricated and exhibited higher conductivity/photoconductivity performance in oleic acid-capped NCs because of a deprotonated carboxyl functional group. We have also introduced a model and mechanism of chemical interface damping in a nonstoichiometric plasmonic semiconductor (Cu2-xS/Se) NC system. This feature article highlights the importance of the surface functionalization of nonstoichiometric plasmonic semiconductors to develop new advanced semiconductor-based devices such as infrared photodetectors, plasmonic solar cells, and efficient NIR phototransistors.

Plasmonic Hot Electron-Mediated Hydrodehalogenation Kinetics on Nanostructured Ag Electrodes.

An attractive field of plasmon-mediated chemical reactions (PMCRs) is developing rapidly, but there is still incomplete understanding of how to control the kinetics of such a reaction related to hot carriers. Here, we chose 8-bromoadenine (8BrAd) as a probe molecule of hot electrons to investigate the influence of the electrode potential, laser wavelength, and power on the PMCR kinetics on silver nanoparticle-modified silver electrodes. Plasmonic hot electron-mediated cleavage of the C-Br bond in 8BrAd has been investigated by combining in situ electrochemical surface-enhanced Raman spectroscopy and density functional theory calculations. The experimental and theoretical results reveal that the energy position of plasmon relaxation-generated hot electrons can be modulated conveniently by applied potentials and laser light. This allows the proposal of a mechanism of modulating the matching energy of the hot electron of plasmon relaxation to promote the efficiency of PMCRs in electrochemical interfaces. Our work will be helpful to design surface plasmon resonance photoelectrochemical reactions on metal electrode surfaces of nanostructures with higher efficiency.

The Inverse Relationship between Metal-Enhanced Fluorescence and Fluorophore-Induced Plasmonic Current

In this work we investigate the relationship between metal-enhanced fluorescence (MEF) and fluorophore-induced plasmonic current (PC). This is accomplished through measurements of both radiative emission (MEF) and direct electrical current generation between discrete metal nanoparticles upon fluorophore excitation (PC). We have conducted these measurements on silver and gold nanoparticle island films, over a range of nanoparticle sizes and spacing in the films. We have observed an inverse relationship in the magnitude of MEF with PC, where larger and more closely spaced metal nanoparticles are found to result in increased PC and subsequently a decreased MEF. We attribute this effect to the relatively high capacitance and low charging energy of large and closely spaced particles, providing an outlet for plasmon relaxation in the form of electron flow and electrical current generation. These results are significant as they open potential for controlling for and the optimization of both MEF and PC.

Anisotropic plasmons due to carrier electrons in Cs-doped hexagonal WO3 studied by momentum transfer resolved electron energy-loss spectroscopy

Cs-doped hexagonal WO3 (CWO) is used as a solar heat-shielding material for windows, in which plasma oscillation due to carrier electrons (carrier plasmon) plays an important role for near infrared scattering. Despite the hexagonal crystal structure of CWO, the anisotropic properties of the carrier plasmons have not been investigated. This study reports the momentum transfer resolved electron energy-loss spectroscopic measurements of CWO to investigate the anisotropic properties of carrier plasmons. The experimental results clarified that the two plasma oscillation modes at 1.2 and 1.8 eV have different excitation properties in CWO. One plasma oscillation at 1.2 eV was excited for q along the ab plane with a large damping effect, which indicated that electron excitations occur for the q//ab plane. Another mode at 1.8 eV was an oscillation excited for q along the c-axis with a small damping effect, i.e., a long plasmon relaxation time. These two modes can be interpreted by the anisotropic energy dispersion of the electronic states around the Fermi level of CWO. Such anisotropic properties of the carrier plasmons led to an accurate understanding of the heat-shielding mechanism.

Photothermal performance of plasmonic patch with gold nanoparticles embedded on polymer matrix

Under light irradiation, gold nanoparticles (AuNPs) reveal the surface plasmon feature, i.e., the occurrence of the collective excitation of the free electrons of NPs. Plasmon relaxation, as well as excitation, induced by light absorption, could be used to increase the local temperature via conversion of light to heat. This photothermal effect can be enhanced by control of the morphology and structure of NPs in the near-infrared (NIR) region. Recently, the use of an NP-composited polymer as a heating patch with a good photothermal performance was suggested for biomedical applications. Herein, AuNPs embedded on polydimethylsiloxane (PDMS) films (Au-PDMS) were successfully prepared with an in-situ synthesis method without a reducing agent. Their photothermal performance was measured with an IR camera under 808 nm NIR irradiation, and a mechanical stretching test for the Au-PDMS films was conducted to investigate the effect of the AuNPs’ density on the photothermal performance. The surface temperature of the films, which reached 120 °C within 1 min, is also adjustable with mechanical stretching (strain change). This is due to the decrease of the AuNPs density with widening interparticle distance between them.

Plasmon localization, plasmon relaxation, and thermal transport in one-dimensional conductors

We study the localization and decay properties as well as the thermal conductance of one-dimensional plasmons. Our model contains a Luttinger-liquid part with spatially random plasmon velocity and interaction parameter as well as a nonlinearity that is cubic in density. The scaling of the decay rate of plasmons is obtained in several regimes. At sufficiently high frequencies, it describes the inelastic life time of localized plasmon excitations that crosses over to the clean result with lowering frequencies. For higher frequencies, we analyze implications of many-body-localization effects that lead to a suppression of the decay rate. We find that the thermal conductance depends in a non-trivial fashion on the system size $L$. Specifically, it scales as $L^{-1/2}$ for sufficiently short wires and crosses over to $L^{-2/3}$ scaling for longer wires.

Holographic plasmon relaxation with and without broken translations

We study the dynamics and the relaxation of bulk plasmons in strongly coupled and quantum critical systems using the holographic framework. We analyze the dispersion relation of the plasmonic modes in detail for an illustrative class of holographic bottom-up models. Comparing to a simple hydrodynamic formula, we entangle the complicated interplay between the three least damped modes and shed light on the underlying physical processes. Such as the dependence of the plasma frequency and the effective relaxation time in terms of the electromagnetic coupling, the charge and the temperature of the system. Introducing momentum dissipation, we then identify its additional contribution to the damping. Finally, we consider the spontaneous symmetry breaking (SSB) of translational invariance. Upon dialing the strength of the SSB, we observe an increase of the longitudinal sound speed controlled by the elastic moduli and a decrease in the plasma frequency of the gapped plasmon. We comment on the condensed matter interpretation of this mechanism.

Morphology induced plasmonic-excitonic interaction revealed by pump-probe spectroscopy

Structure dependent relaxation and recombination dynamics of plasmons in three distinct colloidal plasmonic nanoshapes namely gold nanoflowers (GNF), gold nanopebbles (GNP), gold nanospheres (GNS) and a gold nanoislands film has been investigated with the help of ultrafast pump–probe spectroscopy. The structural transformation study revealed that the geometry plays a vital role in modulating the relaxation time of the plasmons. Further, an organic fluorescent dye (Eosin yellow, EY) is coupled with the aforementioned gold nanoshapes, to decipher the morphology directed excited state intermolecular interaction, amongst the plasmonic–organic hybrids in terms of their temporal and spectral modulations. Indeed, the experimental observations depict a reduction in the fluorescence lifetime of all the hybrids thereby confirming the presence of a nonradiative energy transfer within the hybrids. Variation in the coupling configuration of the EY with the aforementioned gold nanoshapes, lead to a tunable response time, providing a powerful means to alter the optical properties of plasmonic-organic hybrids. Overall, this study may not only help in a better understanding of excited the state dynamics of a coupled hybrid but also pave a way towards the realization of plasmonic-based active photonic devices.

Polarization-dependent ultrafast plasmon relaxation dynamics in nanoporous gold thin films and nanowires

Metal materials structured at nanoscale are extensively used in a variety of applications, including molecular sensing, nanoscale heaters for photothermal therapy, etc. These applications depend on the strong absorption and electric field enhancements associated with localized surface plasmon resonance (LSPR). Despite multiple investigations of LSPR relaxation dynamics in plasmonic metallic nanoparticles (i.e. nanospheres, nanocubes, etc), no detailed studies of porous thin films or nanowires have been reported so far. In this paper, LSPR relaxation dynamics of nanoporous gold thin film, gold nanowires, and nanoporous gold nanowires (structures with the potential for a vast range of sensing and optical applications) were studied by means of transient absorption spectroscopy (TAS). Au and Au/Cu thin films produced by magnetron sputtering deposition over a nanograted silicon substrate enabled the creation of highly organized nanowire arrays of centimetres length. Nanoporous structures were created by the dealloying of Au/Cu alloy. We found that formation of such a subwavelength period grating structure in gold increases the efficiency of hot electron relaxation compared to continuous film, while the porosity of gold nanostructures has the opposite effect. The results also expressed a clear dependence of the TAS signal on the polarization (i.e. orientation of the electric field with respect to the nanoporous gold nanowires) of the pump and probe pulses, compared to non-porous gold nanowires.

Surface plasmon mediated chemical reaction

Surface plasmons are collective oscillations of free electrons at the interface between metal and dielectric. Surface plasmons can break through the diffraction limit of light, because the electromagnetic field is confined in a very small space near the surface of the nanostructure, which provides a possibility for nanometer-scale light manipulation. By using surface plasmon resonance, the local surface electromagnetic field can be strongly enhanced, which can be used to enhance the molecular fluorescence and Raman signals. In addition, the plasmon relaxation induces thermal electrons which can drive the catalytic reaction of surface molecules to achieve a selective catalytic reaction at normal temperature, which is so-called plasmon mediated chemical reaction (or plasmonic catalysis). As a new type of catalytic system, plasmonic catalysis can mediate chemical reactions that are difficult to occur under various conventional conditions. Due to the complexity and diversity of plasmon catalyzed reactions, it is still a huge challenge to fully characterize the reaction kinetics and understand its reaction mechanism. Characterizing the intermediate and final products in the catalytic reaction accurately and obtaining more detailed information in the reaction process are essential for exploring the theoretical mechanism of plasmon catalysis. In this paper, we review the characterization techniques used in plasmon catalysis in detail in the progress of plasmon catalysis. First, the basic concepts of plasmon catalysis and several common catalytic mechanisms are introduced. Second, the Raman spectroscopy, including the application of surface and tip-enhanced Raman spectroscopy in plasmon catalytic in situ monitoring are reviewed. Then, the other techniques such as gas chromatography, gas chromatography-mass spectrometry, high performance liquid chromatography, scanning transmission electron microscopy, scanning tunneling microscopy, scanning electrochemical microscopy and UV-visible absorption spectroscopy for monitoring plasmon catalyzed reaction are introduced in detail. Finally, the characteristics and advantages of these characterization techniques in the study of kinetic catalytic process and catalytic mechanism of plasmon, and the future development and challenge are mentioned and analyzed.

Classical plasma dynamics of Mie-oscillations in atomic clusters

Mie plasmons are of basic importance for the absorption of laser light by atomic clusters. In this work we first review the classical Rayleigh-theory of a dielectric sphere in an external electric field and Thomson’s plum-pudding model applied to atomic clusters. Both approaches allow for elementary discussions of Mie oscillations, however, they also indicate deficiencies in describing the damping mechanisms by electrons crossing the cluster surface. Nonlinear oscillator models have been widely studied to gain an understanding of damping and absorption by outer ionization of the cluster. In the present work, we attempt to address the issue of plasmon relaxation in atomic clusters in more detail based on classical particle simulations. In particular, we wish to study the role of thermal motion on plasmon relaxation, thereby extending nonlinear models of collective single-electron motion. Our simulations are particularly adopted to the regime of classical kinetics in weakly coupled plasmas and to cluster sizes extending the Debye-screening length. It will be illustrated how surface scattering leads to the relaxation of Mie oscillations in the presence of thermal motion and of electron spill-out at the cluster surface. This work is intended to give, from a classical perspective, further insight into recent work on plasmon relaxation in quantum plasmas [1].

Plasmon Modulation Spectroscopy of Noble Metals to Reveal the Distribution of the Fermi Surface Electrons in the Conduction Band

To directly access the dynamics of electron distribution near the Fermi-surface after plasmon excitation, pump-probe spectroscopy was performed by pumping plasmons on noble-metal films and probing the interband transition. Spectral change in the interband transitions is sensitive to the electron distribution near the Fermi-surface, because it involves the d valence-band to the conduction band transitions and should reflect the k-space distribution dynamics of electrons. For the continuous-wave pump and probe experiment, the plasmon modulation spectra are found to differ from both the current modulation and temperature difference spectra, possibly reflecting signatures of the plasmon wave function. For the femtosecond-pulse pump and probe experiment, the transient spectra agree well with the known spectra upon the excitation of the respective electrons resulting from plasmon relaxation, probably because the lifetime of plasmons is shorter than the pulse duration.