Collective Plasmon Excitations Research Articles

Ultrahigh resolution x-ray Thomson scattering measurements at the European X-ray Free Electron Laser

Using an ultrahigh resolution (ΔE∼0.1eV) setup to measure electronic features in x-ray Thomson scattering (XRTS) experiments at the European XFEL in Germany, we have studied the collective plasmon excitation in aluminium at ambient conditions, which we can measure very accurately even at low momentum transfers. As a result, we can resolve previously reported discrepancies between time-dependent density functional theory simulations and experimental observations. The demonstrated capability for high-resolution XRTS measurements will be a game changer for the diagnosis of experiments with matter under extreme densities, temperatures, and pressures, and unlock the full potential of state-of-the-art x-ray free electron laser (XFEL) facilities to study planetary interior conditions, to understand inertial confinement fusion applications, and for material science and discovery. Published by the American Physical Society 2024

Excitation signatures of isochorically heated electrons in solids at finite wave number explored from first principles

Ultrafast heating of solids with modern x-ray free electron lasers (XFELs) leads to a unique set of conditions characterized by the simultaneous presence of heated electrons in a cold ionic lattice. In this work, we analyze the effect of electronic heating on the dynamic structure factor (DSF) in bulk aluminum (Al) with a face-centered cubic lattice and in silicon (Si) with a crystal diamond structure using first-principles linear-response time-dependent density functional theory simulations. We find a thermally induced red shift of the collective plasmon excitation in both materials. In addition, we show that the heating of the electrons in Al can lead to the formation of a double-plasmon peak due to the extension of the Landau damping region to smaller wave numbers. Finally, we demonstrate that thermal effects generate a measurable and distinct signature (peak-valley structure) in the DSF of Si at small frequencies. Our simulations indicate a variety of new features in the spectrum of x-ray-driven solids, specifically at finite momentum transfer, which can be probed in upcoming x-ray Thomson scattering experiments at various XFEL facilities. Published by the American Physical Society 2024

Theoretical investigation on the optical absorption spectra in cyclo[[formula omitted]]carbons ([formula omitted] 10, 14, 18)

The optical absorption spectra of cyclo[n]carbons (n= 10, 14, 18) are investigated in the framework of time-dependent density functional theory. The collective plasmon excitations well develop as the increases of the ring size and the symmetry group of cyclo[n]carbons. An increase in intensity for the main peaks with the growing number of atoms in cyclo[n]carbons is observed. With the increase of the radius of the monocyclic ring, as more electrons participate in the dipole oscillation the main excitation peaks are red-shifted to the lower energy. The highly symmetrical structures of cyclo[n]carbons (Dnh) possess degenerate levels, leading to simpler spectra with fewer peaks. The Fourier transform of the induced electron density of the cyclo[n]carbons (n= 10, 14, 18) is investigated at the excitation frequencies.

Revealing quasi-excitations in the low-density homogeneous electron gas with model exchange–correlation kernels

Time-dependent density functional theory within the linear response regime provides a solid mathematical framework to capture excitations. The accuracy of the theory, however, largely depends on the approximations for the exchange–correlation (xc) kernels. Away from the long-wavelength (or q = 0 short wave-vector) and zero-frequency (ω = 0) limit, the correlation contribution to the kernel becomes more relevant and dominant over exchange. The dielectric function, in principle, can encompass xc effects relevant to describe low-density physics. Furthermore, besides collective plasmon excitations, the dielectric function can reveal collective electron–hole excitations, often dubbed “ghost excitons.” Besides collective excitons, the physics of the low-density regime is rich, as exemplified by a static charge-density wave that was recently found for rs > 69, and was shown to be associated with softening of the plasmon mode. These excitations are seen to be present in much higher density 2D homogeneous electron gases of rs ≳ 4. In this work, we perform a thorough analysis with xc model kernels for excitations of various nature. The uniform electron gas, as a useful model of real metallic systems, is used as a platform for our analysis. We highlight the relevance of exact constraints as we display and explain screening and excitations in the low-density region.

Emergent plasmonic excitations in Mexican-hat and bell-shaped bands of hybridized Dirac electrons in graphene/topological insulator heterostructures

Stacking a graphene monolayer onto a three-dimensional topological insulator results in a van der Waals heterostructure that can serve as a versatile platform for rich emergent exotic physics. In particular, the Dirac electrons of the graphene and that of the two-dimensional surface states of the topological insulator hybridize effectively, leading to the emergence of two distinct electronic bands around the Fermi level, with respective Mexican-hat and bell shapes. In this paper, we explore the emergent collective plasmonic excitations in the representative heterostructure of graphene/${\mathrm{Sb}}_{2}{\mathrm{Te}}_{3}$, combining first-principles calculations and low-energy effective Hamiltonian descriptions. We discover two different plasmon modes of the system, and our band-resolved analysis allows us to attribute the two modes to the intraband transitions within the Mexican-hat and bell-shaped bands, respectively. We also analyze the relative strengths and damping rates of the plasmon modes upon variations of the bias potential across the heterojunction, enabling potential experimental detections of those collective excitations. These findings provide alternate avenues for regulating the electronic states and plasmonic excitations in the hybridized Dirac electron systems for potential device applications.

Theory of plasmonic edge states in chiral bilayer systems

We analytically describe the plasmonic edge modes for an interface that involves the twisted bilayer graphene (TBG) or other similar Moire van der Waals heterostructure. For this purpose, we employ a spatially homogeneous, isotropic and frequency-dependent tensor conductivity which in principle accounts for electronic and electrostatic interlayer couplings. We predict that the edge mode dispersion relation explicitly depends on the chiral response even in the nonretarded limit, in contrast to the collective bulk plasmonic excitations in the TBG. We obtain a universal function for the dispersion of the optical edge plasmon in the paramagnetic regime. This implies a correspondence of the chiral-TBG optical plasmon to a magnetoplasmon of a single sheet, and chirality is interpreted as an effective magnetic field. The chirality also opens up the possibility of nearly undamped acoustic modes in the paramagnetic regime. Our results may guide future near-field nanoscopy for van der Waals heterostructures. In our analysis, we retain the long-range electrostatic interaction, and apply the Wiener-Hopf method to a system of integral equations for the scalar potentials of the two layers.

Plasmon Coupling in DNA-Assembled Silver Nanoclusters.

Quantum-size metal clusters with multiple delocalized electrons could support collective plasmon excitation, and thus, theoretically, coupling of plasmons in the few-atom limit might exist between assembled metal clusters, while currently few experimental observations about this phenomenon have been reported. Here we examined the optical absorption of DNA-templated Ag nanoclusters (DNA-AgNCs) assembled through DNA hybridization and found their absorption peaks were sensitive to the assembled distances, which share common characteristics with classical plasmon coupling. Dipolar charge distribution, multiple transition contributed optical absorption, and strongly enhanced electric field simulated by time-dependent density functional theory (TDDFT) indicated the origin of the absorption of individual DNA-AgNCs is a plasmon. The consistency of the peak-shifting trend between experimental and simulation results for assembled DNA-AgNCs suggested the possible presence of plasmon coupling. Our data imply the possibility for quantum-size structures to support plasmon coupling and also show that DNA-AgNCs possess the potential to be promising materials for construction of plasmon-coupling devices with ultrasmall size, site-specific and stoichiometric binding abilities, and biocompatibility.

Kinetic Processes in Fermi–Luttinger Liquids

In this work we discuss extensions of the pioneering analysis by Dzyaloshinskii and Larkin of correlation functions for one-dimensional Fermi systems, focusing on the effects of quasiparticle relaxation enabled by a nonlinear dispersion. Throughout the work we employ both, the weakly interacting Fermi gas picture and nonlinear Luttinger liquid theory to describe attenuation of excitations and explore the fermion-boson duality between both approaches. Special attention is devoted to the role of spin-exchange processes, effects of interaction screening, and integrability. Thermalization rates for electron- and hole-like quasiparticles, as well as the decay rate of collective plasmon excitations and the momentum space mobility of spin excitations are calculated for various temperature regimes. The phenomenon of spin-charge drag is considered and the corresponding momentum transfer rate is determined. We further discuss how momentum relaxation due to several competing mechanisms, viz. triple electron collisions, electron-phonon scattering, and long-range inhomogeneities affect transport properties, and highlight energy transfer facilitated by plasmons from the perspective of the inhomogeneous Luttinger liquid model. Finally, we derive the full matrix of thermoelectric coefficients at the quantum critical point of the first conductance plateau transition, and address magnetoconductance in ballistic semiconductor nanowires with strong Rashba spin-orbit coupling.

KINETIC PROCESSES IN FERMI-LUTTINGER LIQUIDS

In this work we discuss extensions of the pioneering analysis by Dzyaloshinskii and Larkin of correlation functions for one-dimensional Fermi systems, focusing on the effects of quasiparticle relaxation enabled by a nonlinear dispersion. Throughout the work we employ both, the weakly interacting Fermi gas picture and nonlinear Luttinger liquid theory to describe attenuation of excitations and explore the fermion-boson duality between both approaches. Special attention is devoted to the role of spin-exchange processes, effects of interaction screening, and integrability. Thermalization rates for electron- and hole-like quasiparticles, as well as the decay rate of collective plasmon excitations and the momentum space mobility of spin excitations are calculated for various temperature regimes. The phenomenon of spin-charge drag is considered and the corresponding momentum transfer rate is determined. We further discuss how momentum relaxation due to several competing mechanisms, viz. triple electron collisions, electron-phonon scattering, and long-range inhomogeneities affect transport properties, and highlight energy transfer facilitated by plasmons from the perspective of the inhomogeneous Luttinger liquid model. Finally, we derive the full matrix of thermoelectric coefficients at the quantum critical point of the first conductance plateau transition, and address magnetoconductance in ballistic semiconductor nanowires with strong Rashba spin-orbit coupling.

Emergent chiroptical properties in supramolecular and plasmonic assemblies.

This tutorial provides a comprehensive description of the origin of chiroptical properties of supramolecular and plasmonic assemblies in the UV-visible region of the electromagnetic spectrum. The photophysical concepts essential for understanding chiroptical signatures are presented in the first section. Just as the oscillator strength (a positive quantity) is related to absorption, the rotational strength (either a positive or a negative quantity) defines the emergence of chiroptical signatures in molecular/plasmonic systems. In supramolecular systems, induced circular dichroism (ICD) originates through the off-resonance coupling of transition dipoles in chiral inclusion complexes, while exciton coupled circular dichroism (ECD) originates through the on-resonance exciton coupling of transition dipoles in chiral assemblies resulting in the formation of a bisignated CD signal. In bisignated ECD spectra, the sign of the couplet is determined not only by the handedness of chiral supramolecular assemblies, but also by the sign of the interaction energy between transition dipoles. Plasmonic chirality is briefly addressed in the last section, focusing on inherent chirality, induced chirality, and surface plasmon-coupled circular dichroism (SP-CD). The oscillator strength is of the order of 1 in molecular systems, while it becomes very large (104-105) in plasmonic systems due to the collective plasmonic excitations, resulting in intense CD signals, which can be exploited for the design of plasmonic metamaterial platforms for chiral sensing applications.

Plasmonic modes in cylindrical nanoparticles and dimers.

We present analytical expressions for the resonance frequencies of the plasmonic modes hosted in a cylindrical nanoparticle within the quasi-static approximation. Our theoretical model gives us access to both the longitudinally and transversally polarized dipolar modes for a metallic cylinder with an arbitrary aspect ratio, which allows us to capture the physics of both plasmonic nanodisks and nanowires. We also calculate quantum mechanical corrections to these resonance frequencies due to the spill-out effect, which is of relevance for cylinders with nanometric dimensions. We go on to consider the coupling of localized surface plasmons in a dimer of cylindrical nanoparticles, which leads to collective plasmonic excitations. We extend our theoretical formalism to construct an analytical model of the dimer, describing the evolution with the inter-nanoparticle separation of the resultant bright and dark collective modes. We comment on the renormalization of the coupled mode frequencies due to the spill-out effect, and discuss some methods of experimental detection.

Monodisperse Gold Cuboctahedral Nanocrystals Directly Synthesized in Reverse Micelles: Preparation, Colloidal Dispersion in Organic Solvents and Water, Reversible Self-Assembly and Plasmonic Properties.

The synthesis of organic-solvent-dispersible gold nanoparticles in reverse micelles of didodecyldimethylammonium bromide (DDAB) is revisited in the present investigation. Some parameters of synthesis, specifically the reaction volume and the concentration of the reducing agent, were slightly modified obtaining directly monodisperse gold nanocrystals (AuNCs) without the need to use additional active surfactants or additional treatments such as digestive ripening. Interestingly, most of the obtained AuNCs display the same exposed crystalline faces composed of six bounding facets (four {111} faces and two {002} faces), corresponding to single-crystalline face-centered cubic nanoparticles with a cuboctahedron shape. When these AuNCs are subsequently functionalized with 1-decanethiol (C10H21SH) or 1-dodecanethiol (C12H25SH), they don't experience significant changes in their size or crystalline texture, however, they self-aggregate directly in the suspension at room temperature into faceted supramolecular structures and exhibit collective plasmonic excitations. Such self-organization is reversible under heating treatments allowing the observation of the influence of the AuNCs aggregation state on their plasmonic properties. Fourier transform infrared spectroscopy reveals that thiols only replace partially the DDAB molecules, and thus, DDAB molecules remain present in the thiol-capped AuNCs. To turn the thiol-capped nanocrystals into water-dispersible nanocrystals and extend their technological potential, they are stabilized with poloxamer 407 obtaining highly stable purple colloids in water.

Nonlinear Plasmonic Photoelectron Response of Ag(111).

Photons can excite collective and single-particle excitations in metals; the collective plasmonic excitations are of keen interest in physics, chemistry, optics, and nanotechnology because they enhance coupling of electromagnetic energy and can drive nonlinear processes in electronic materials, particularly where their dielectric function ϵ(ω) approaches zero. We investigate the nonlinear angle-resolved two-photon photoemission (2PP) spectroscopy of the Ag(111) surface through the ϵ(ω) near-zero region. In addition to the Einsteinian single-particle photoemission, the 2PP spectra report unequivocal signatures of nonlocal dielectric, plasmonically enhanced, excitation processes.

AbInitio Lifetime and Concomitant Double-Excitation Character of Plasmons at Metallic Densities.

The accurate calculation of excited state properties of interacting electrons in the condensed phase is an immense challenge in computational physics. Here, we use state-of-the-art equation-of-motion coupled-cluster theory with single and double excitations (EOM-CCSD) to calculate the dynamic structure factor, which can be experimentally measured by inelastic x-ray and electron scattering. Our calculations are performed on the uniform electron gas at densities corresponding to Wigner-Seitz radii of r_{s}=5, 4, and 3 corresponding to the valence electron densities of common metals. We compare our results to those obtained using the random-phase approximation (RPA), which is known to provide a reasonable description of the collective plasmon excitation and which resums only a small subset of the polarizability diagrams included in EOM-CCSD. We find that EOM-CCSD, instead of providing a perturbative improvement on the RPA plasmon, predicts a many-state plasmon resonance, where each contributing state has a double-excitation character of 80% or more. This finding amounts to an abinitio treatment of the plasmon linewidth, which is in good quantitative agreement with previous diagrammatic calculations, and highlights the strongly correlated nature of lifetime effects in condensed-phase electronic structure theory.

A theoretical study of collective plasmonic excitations in double-layer silicene at finite temperature

We explore the temperature-dependent plasmonic modes of an n-doped double-layer silicene system which is composed of two spatially separated single layers of silicene with a distance large enough to prevent interlayer electron tunneling. By applying an externally applied electric field, we numerically obtain the poles of the loss function within the so-called random phase approximation to investigate the effects of temperature and geometry on the plasmon branches in three different regimes: topological insulator, valley-spin polarized metal, and band insulator. Also, we present the finite-temperature numerical results along with the zero-temperature analytical ones to support a discussion of the distinct effects of the external electric field and temperature on plasmon dispersion. Our results show that at zero temperature both the acoustic and optical modes decrease when the applied electric field is increased and experience a discontinuity at the valley-spin polarized metal phase as the system transitions from a topological insulator to a band insulator. At finite temperature, the optical plasmons are damped around this discontinuity, and the acoustic modes may exhibit a continuous transition. Moreover, while the optical branch of plasmons changes non-monotonically and noticeably with temperature, the acoustic branch dispersion displays a negligible growth with temperature for all phases of silicene. Furthermore, our finite-temperature results indicate that the dependency of two plasmonic branches on the interlayer separation is not affected by temperature at long wavelengths; the acoustic mode energy varies slightly with an increase in the interlayer distance, whereas the optical mode remains unchanged.

Generation of hot electrons in nanostructures incorporating conventional and unconventional plasmonic materials.

The generation of energetic electrons is an effect occurring in any plasmonic nanostructure. However, the number of electrons with high energies generated optically in a plasmonic nanostructure can be relatively small. This is an intrinsic property of the collective plasmon excitations in a Fermi gas of electrons. But the choices of material and geometry have a great impact on the generation rate, and are therefore crucial for designing a nanostructure with a large rate of generation of energetic (hot) electrons. Here we test different plasmonic materials from the point of view of the generation of hot electrons (HEs). Our choice of materials includes both strongly-plasmonic materials (Au, Ag, Cu and Al) and crystals with strongly broadened plasmonic resonances (Pt, TiN and ZrN). Regarding the choice of geometry, we consider two types of nanostructures, single nanocrystals deposited over a dielectric substrate and metastructure absorbers, observing interesting opto-electronic properties. For single nanocrystals, the rate of HE generation is strongly material-dependent since the HE generation rate strongly depends on several physical parameters such as plasmonic enhancement, plasmonic resonance wavelength, Fermi energy, etc. Interestingly, the plasmonic meta-absorbers exhibit a different behaviour. The strongly-plasmonic metals, such as Au, Ag, Cu or Al, show very similar performances, while the materials with damped plasmon resonances demonstrate diverse and reduced rates of HE generation. The physical reason for these different behaviours lies in the dielectric functions of these materials. In the metastructures, plasmonic resonances are in the infrared region and the strongly-plasmonic materials behave as an almost ideal metal, whereas the second group of materials exhibits strong dissipation. This makes the responses from the metastructures made of crystals with damped plasmons strongly dependent on the choice of material. The physical principles described in our study can be useful for designing metastructures and nanodevices based on HEs, which can be used in photo-chemistry and opto-electronics.

Optical absorption properties of few-layer phosphorene

We investigate the optical absorption and transmission of few-layer phosphorene in the framework of ab initio density functional simulations and many-body perturbation theory at the level of random phase approximation. In bilayer phosphorene, the optical transition of the valence band to the conduction band appears along the armchair direction at about 0.72 eV, while it is absent along the zigzag direction. This phenomenon is consistent with experimental observations. The angle-resolved optical absorption in few-layer phosphorene shows that it is transparent when illuminated by near grazing incidence of light. Also, there is a general trend of an increase in the absorption by increasing the number of layers. Our results show that the bilayer phosphorene exhibits greater absorbance compared to that of bilayer graphene in the ultraviolet region. Moreover, the maximal peak in the calculated absorption of bilayer MoS2 is in the visible region, while bilayer graphene and phosphorene are transparent. Besides, the collective electronic excitations of few-layer phosphorene are explored. An optical mode (in-phase mode) that follows a low-energy \sqrt q dependence for all structures, and another which is a damped acoustic mode (out-of-phase mode) with linear dispersion for multilayer phosphorene are obtained. The anisotropy of the band structure of few-layer phosphorene along the armchair and zigzag directions is manifested in the collective plasmon excitations.

Crossover from lattice to plasmonic polarons of a spin-polarised electron gas in ferromagnetic EuO

Strong many-body interactions in solids yield a host of fascinating and potentially useful physical properties. Here, from angle-resolved photoemission experiments and ab initio many-body calculations, we demonstrate how a strong coupling of conduction electrons with collective plasmon excitations of their own Fermi sea leads to the formation of plasmonic polarons in the doped ferromagnetic semiconductor EuO. We observe how these exhibit a significant tunability with charge carrier doping, leading to a polaronic liquid that is qualitatively distinct from its more conventional lattice-dominated analogue. Our study thus suggests powerful opportunities for tailoring quantum many-body interactions in solids via dilute charge carrier doping.

Substantially Enhancing Quantum Coherence of Electrons in Graphene via Electron-Plasmon Coupling.

The interplays between different quasiparticles in solids lay the foundation for a wide spectrum of intriguing quantum effects, yet how the collective plasmon excitations affect the quantum transport of electrons remains largely unexplored. Here we provide the first demonstration that when the electron-plasmon coupling is introduced, the quantum coherence of electrons in graphene is substantially enhanced with the quantum coherence length almost tripled. We further develop a microscopic model to interpret the striking observations, emphasizing the vital role of the graphene plasmons in suppressing electron-electron dephasing. The novel and transformative concept of plasmon-enhanced quantum coherence sheds new insight into interquasiparticle interactions, and further extends a new dimension to exploit nontrivial quantum phenomena and devices in solid systems.

Topological collective plasmons in bipartite chains of metallic nanoparticles

We study a bipartite linear chain constituted by spherical metallic nanoparticles, where each nanoparticle supports a localized surface plasmon. The near-field dipolar interaction between the localized surface plasmons gives rise to collective plasmons, which are extended over the whole nanoparticle array. We derive analytically the spectrum and the eigenstates of the collective plasmonic excitations. At the edge of the Brillouin zone, the spectrum is of a pseudorelativistic nature similar to that present in the electronic band structure of polyacetylene. We find the effective Dirac Hamiltonian for the collective plasmons and show that the corresponding spinor eigenstates represent one-dimensional Dirac-like massive bosonic excitations. Therefore, the plasmonic lattice exhibits similar effects to those found for electrons in one-dimensional Dirac materials, such as the ability for transmission with highly suppressed backscattering due to Klein tunneling. We also show that the system is governed by a nontrivial Zak phase, which predicts the manifestation of edge states in the chain. When two dimerized chains with different topological phases are connected, we find the appearance of the bosonic version of a Jackiw-Rebbi midgap state. We further investigate the radiative and nonradiative lifetimes of the collective plasmonic excitations and comment on the challenges for experimental realization of the topological effects found theoretically.