Electron Dynamics Research Articles

Electronic dynamics of donor–bridge–acceptor system with a bridge impurity incorporated in dissipative environments

Electronic dynamics of Donor–Bridge–Acceptor system with a bridge impurity incorporated in dissipative environments is studied taking advantage of the quasi-adiabatic propagator path integral approach in this article. An impurity site is introduced in the center of bridge chain of the system. The numerical calculations indicate the electron transfer rates of the system are changed when the energy gap between the center site (impurity site) and other bridge sites increased from −2.5 to 2.5 eV, the relaxation rates decrease and the dephasing rates increase as the energy gap increases, respectively under the same environment factors (e.g. temperature and system–environment coupling). However, the electron transfer mechanism of the system is hardly affected when the bridge impurity energy is increased in the range of ±21% relative to the other bridge energy, and the occupation populations of bridge chain are not more than 10%, which means the superexchange mechanism also works well within the context of this study.

Electronic dynamics through conical intersections via non-Markovian stochastic Schrödinger equation with complex modes.

Conical intersections (CIs) play a crucial role in photochemical reactions, offering an efficient channel for ultrafast non-adiabatic relaxation of excited states. This significantly influences the reaction pathways and the resulting products. In this work, we utilize the non-Markovian stochastic Schrödinger equation with complex modes method to explore the dynamics of electronic transitions through conical intersections (CIs) in pyrazine. The linear vibronic coupling model serves as the foundational framework, incorporating both intra-state and inter-state electron-vibrational interactions. The dynamics of the excited electronic transitions are analyzed across varying strengths of system-bath coupling and different bath relaxation times. The accuracy of this method is demonstrated by comparing its predictions with those from the hierarchical equations of motion method.

Harnessing collisional nonlinearity for enhanced harmonic generation by ultraviolet plasmonic nanoparticles.

We investigate the contribution of inelastic electron collisions to nonlinear (NL) dynamics in ultraviolet plasmonic nanoparticles, exploring their potential for harmonic generation. Employing the Landau weak coupling formalism to model radiation-driven electron dynamics in sodium and aluminum, we account for both electron-electron and electron-phonon scattering processes by a set of hydrodynamic equations, which we solve perturbatively to obtain third-order NL susceptibilities. Furthermore, we model high harmonic generation enhanced by localized surface plasmons in nanospheres composed of such poor metals, demonstrating their efficient operation for extreme ultraviolet generation. Our investigation reveals that plasmonic nanospheres composed of sodium and aluminum produce a large field intensity enhancement of ≃103-105, boosting the harmonic generation process. Our findings indicate that poor metals hold great promise for advanced extreme ultraviolet nano-sources with potential applications in nano-spectroscopy.

Regarding the relativistic electron dynamics in the outer radiation belt: a historical view

Regarding the relativistic electron dynamics in the outer radiation belt: a historical view

Resonant inelastic x-ray scattering in warm-dense Fe compounds beyond the SASE FEL resolution limit

Resonant inelastic x-ray scattering (RIXS) is a widely used spectroscopic technique, providing access to the electronic structure and dynamics of atoms, molecules, and solids. However, RIXS requires a narrow bandwidth x-ray probe to achieve high spectral resolution. The challenges in delivering an energetic monochromated beam from an x-ray free electron laser (XFEL) thus limit its use in few-shot experiments, including for the study of high energy density systems. Here we demonstrate that by correlating the measurements of the self-amplified spontaneous emission (SASE) spectrum of an XFEL with the RIXS signal, using a dynamic kernel deconvolution with a neural surrogate, we can achieve electronic structure resolutions substantially higher than those normally afforded by the bandwidth of the incoming x-ray beam. We further show how this technique allows us to discriminate between the valence structures of Fe and Fe2O3, and provides access to temperature measurements as well as M-shell binding energies estimates in warm-dense Fe compounds.

Unconventional Thermophotonic Charge Density Wave.

Charge-order states of broken symmetry, such as charge density wave (CDW), are able to induce exceptional physical properties, however, the precise understanding of the underlying physics is still elusive. Here, we combine fluctuational electrodynamics and density functional theory to reveal an unconventional thermophotonic effect in CDW-bearing TiSe_{2}, referred to as thermophotonic-CDW (tp-CDW). The interplay of plasmon polariton and CDW electron excitations give rise to an anomalous negative temperature dependency in thermal photons transport, offering an intuitive fingerprint for a transformation of the electron order. Additionally, the demonstrated nontrivial features of tp-CDW transition hold promise for a controllable manipulation of heat flow, which could be extensively utilized in various fields such as thermal science and electron dynamics, as well as in next-generation energy devices.

Ultrafast Two-Color X-Ray Emission Spectroscopy Reveals Excited State Landscape in a Base Metal Dyad.

Effective photoinduced charge transfer makes molecular bimetallic assemblies attractive for applications as active light-induced proton reduction systems. Developing competitive base metal dyads is mandatory for a more sustainable future. However, the electron transfer mechanisms from the photosensitizer to the proton reduction catalyst in base metal dyads remain so far unexplored. A Fe─Co dyad that exhibits photocatalytic H2 production activity is studied using femtosecond X-ray emission spectroscopy, complemented by ultrafast optical spectroscopy and theoretical time-dependent DFT calculations, to understand the electronic and structural dynamics after photoexcitation and during the subsequent charge transfer process from the FeII photosensitizer to the cobaloxime catalyst. This novel approach enables the simultaneous measurement of the transient X-ray emission at the iron and cobalt K-edges in a two-color experiment. With this methodology, the excited state dynamics are correlated to the electron transfer processes, and evidence of the Fe→Co electron transfer as an initial step of proton reduction activity is unraveled.

Manifestation of the quantum metric in chiral lattice systems

Recent years have seen a surge in research on the role of quantum geometry in condensed matter physics. For instance, the Aharonov-Bohm effect is a physical phenomenon where the vector potential induces a phase shift of electron wavepackets in regions with zero magnetic fields due to an obstruction in space associated with a magnetic flux. A similar effect can be observed in solid-state systems, where the topology of the Berry connection can influence electron dynamics. These are paradigmatic examples of how the dynamics can be affected by the system’s geometry. Here, we show that in chiral-symmetric processes the quantum metric has a measurable effect on the mean chiral displacement of delocalized wavefunctions. This finding is supported by a photonic experiment realizing a topological quantum walk and demonstrates an effect that can be attributed directly to the geometry of the state space.

Near-field induced local excitation dynamics of Na10 and Na10-N2 from real-time TDDFT.

Electron dynamics of the Na10 chain and the Na10-N2 complex locally excited by an atomistic optical near-field are investigated using real-time time-dependent density functional theory calculations on real-space grids. Ultrafast laser pulses were used to simulate the near-field excitation under on- and off-resonance conditions. Off-resonance excitation did not lead to the propagation of the excitation through the Na10 chain. In contrast, under the resonance conditions, the excited state is delocalized over the entire Na chain. Analysis of the local dipole moment of each atom in Na10 indicates that this behavior is consistent with the transition density. Adding an N2 molecule to the opposite end of the local excitation region results in energy transfer via the Na10 chain. The energy transfer efficiency of the N2 molecule is well correlated with the absorption spectrum of Na10. The present study paves the way for realizing remote excitation and photonic devices at the atomic scale.

Ultrafast dynamics and mechanism of structure formation in titanium nitride upon femtosecond laser irradiation for plasmonic enhanced photothermal effect

Femtosecond laser has great potential in controlling the surface structure of titanium nitride (TiN) to promote plasmonic photothermal effect. Studying the mechanism of femtosecond laser irradiation on the surface and inside of the TiN benefits the photothermal microdevices. Ultrafast dynamics of electrons and lattices of TiN films with different thicknesses were first studied through pump-probe technique, which found that the electron density is easier to reach the maximum on the surface than the electrons in deep-layers. High-frequency ripple was formed by tiny nucleation resulted from weak eruption of surface material on the thin TiN film, and low-frequency ripple was emerged through large nucleation of material clusters simultaneously on the thick TiN film. The blue shift and intensity changes of Raman peak on 200 nm TiN film indicate the heterogeneous structure changed from TiN to TiN0.26 after laser processing, and the vacancy occupies causes the lattice vibration weakened. The 200 nm TiN film after processing shows enhanced local surface plasma resonance absorption effect, which induced the reflectivity is reduced by 30 %, and the light and thermal conversion efficiency increased by 80 %. These results proved the promising utilization of TiN in biological and medical applications, energy collection and thermal auxiliary magnetic records.

High-harmonic spin-orbit angular momentum generation in crystalline solids preserving multiscale dynamical symmetry.

Symmetries essentially provide conservation rules in nonlinear light-matter interactions and facilitate control and understanding of photon conversion processes or electron dynamics. Since anisotropic solids have rich symmetries, they are strong candidates for controlling both optical micro- and macroscale structures, namely, spin angular momentum (circular polarization) and orbital angular momentum (spiral wavefront), respectively. Here, we show structured high-harmonic generation linked to the anisotropic symmetry of a solid. By strategically preserving a dynamical symmetry arising from the spin-orbit interaction of light, we generate multiple orbital angular momentum states in high-order harmonics. The experimental results exhibit the total angular momentum conservation rule of light even in the extreme nonlinear region, which is evidence that the mechanism originates from a dynamical symmetry. Our study provides a deeper understanding of multiscale nonlinear optical phenomena and a general guideline for using electronic structures to control structured light, such as through Floquet engineering.

Femtosecond Core-Level Spectroscopy Reveals Involvement of Triplet States in the Gas-Phase Photodissociation of Fe(CO)5.

Excitation of iron pentacarbonyl [Fe(CO)5], a prototypical photocatalyst, at 266 nm causes the sequential loss of two CO ligands in the gas phase, creating catalytically active, unsaturated iron carbonyls. Despite numerous studies, major aspects of its ultrafast photochemistry remain unresolved because the early excited-state dynamics have so far eluded spectroscopic observation. This has led to the long-held assumption that ultrafast dissociation of gas-phase Fe(CO)5 proceeds exclusively on the singlet manifold. Herein, we present a combined experimental-theoretical study employing ultrafast extreme ultraviolet transient absorption spectroscopy near the Fe M2,3-edge, which features spectral evolution on 100 fs and 3 ps time scales, alongside high-level electronic structure theory, which enables characterization of the molecular geometries and electronic states involved in the ultrafast photodissociation of Fe(CO)5. We assign the 100 fs evolution to spectroscopic signatures associated with intertwined structural and electronic dynamics on the singlet metal-centered states during the first CO loss and the 3 ps evolution to the competing dissociation of Fe(CO)4 along the lowest singlet and triplet surfaces to form Fe(CO)3. Calculations of transient spectra in both singlet and triplet states as well as spin-orbit coupling constants along key structural pathways provide evidence for intersystem crossing to the triplet ground state of Fe(CO)4. Thus, our work presents the first spectroscopic detection of transient excited states during ultrafast photodissociation of gas-phase Fe(CO)5 and challenges the long-standing assumption that triplet states do not play a role in the ultrafast dynamics.

Self-consistent effects in the ponderomotive acceleration of electron beams

In the present work, we extend the results of a previous investigation on the dynamics of electrons under the action of an inverse free-electron-laser scheme (Almansa et al., Phys. Plasmas, vol. 26, 2019, 033105). While the former work examined electrons as single test particles subject to the combined action of a modulated wiggler plus a laser field, we now look at electrons as composing a particle beam, where collective space-charge effects are relevant and included in the analysis. Our previous work showed that effective acceleration is achieved when the initial velocities of the particles are close enough to the phase velocity of the beat-wave mode formed by the laser and the wiggler fields. Electrons are then initially accelerated by a ponderomotive uphill effect generated by the beat mode and, once reaching the phase velocity of the beat, undergo a final strong resonant acceleration step resembling a catapult effect. The present work shows that, under proper conditions, space-charge effects play a similar role as the initial (or injected) velocity of the beam. Even if acceleration is absent when space charge is neglected, it may be present and effective when charge effects are taken into account. We also discuss how far the space charge can grow without affecting the sustainability of the acceleration process.

Time-resolved ARPES with probe energy of 6.0 eV and tunable MIR pump at 250 kHz

In this paper, we present a laser source designed specifically for time- and angle-resolved photoemission spectroscopy (TR-ARPES) investigations of light-induced electron dynamics in quantum materials. Our laser source is based on a ytterbium-doped laser that seeds an optical parametric amplifier (OPA) followed by a difference frequency generation (DFG) stage. This configuration enables the generation of tunable near-infrared and mid-infrared laser pulses (1.5 to 8 μm - 0.82 to 0.15 eV) at 250 kHz of repetition rate, serving as the pump for TR-ARPES measurements. The remaining energy of the laser is used to generate the ultraviolet 6 eV probe pulses, which prompt the material to emit photoelectrons. We demonstrate the long-term stability of the source, as well as the characterization of the beam profiles and pulse durations. Additionally, we present preliminary TR-ARPES results obtained on Bi2Te3, a prototypical 3D topological insulator. This paper illustrates the capability of our laser source to probe electronic dynamics in quantum materials.

High-Order Harmonic Generation in Photoexcited Three-Dimensional Dirac Semimetals.

High-order harmonic generation (HHG) in condensed matter is highly important for potential applications in various fields, such as materials characterization, all-optical switches, and coherent light source generation. Linking HHG to the properties or dynamic processes of materials is essential for realizing these applications. Here, a bridge has been built between HHG and the transient properties of materials through the engineering of interband polarization in a photoexcited three-dimensional Dirac semimetal (3D-DSM). It has been found that HHG can be efficiently manipulated by the electronic relaxation dynamics of 3D-DSM on an ultrafast time scale of several hundred femtoseconds. Furthermore, time-resolved HHG (tr-HHG) has been demonstrated to be a powerful spectroscopy method for tracking electron relaxation dynamics, enabling the identification of electron thermalization and electron-phonon coupling processes and the quantitative extraction of electron-phonon coupling strength. This demonstration provides insights into the active control of HHG and measurements of the electron dynamics.

A flexible beamline combining XUV attosecond pulses with few-femtosecond UV and near-infrared pulses for time-resolved experiments.

We describe a beamline where few-femtosecond ultraviolet (UV) pulses are generated and synchronized to few-cycle near-infrared (NIR) and extreme ultraviolet (XUV) attosecond pulses. The UV light is obtained via third-harmonic generation in argon or neon gas when focusing a phase-stabilized NIR driving field inside a glass cell that was designed to support high pressures for enhanced conversion efficiency. A recirculation system allows reducing the large gas consumption required for the nonlinear process. Isolated attosecond pulses are generated using the polarization gating technique, and the photon spectrometer employed to characterize the XUV radiation consists of a new design based on the combination of a spherical varied-line-space grating and a cylindrical mirror. This design allows for compactness while providing a long entrance arm for integrating different experimental chambers. The entire interferometer is built under vacuum to prevent both absorption of the XUV light and dispersion of the UV pulses, and it is actively stabilized to ensure an attosecond delay stability during experiments. This table-top source has been realized with the aim of investigating UV-induced electron dynamics in neutral states of bio-relevant molecules, but it also offers the possibility to implement a manifold of novel time-resolved experiments based on photo-ionization/excitation of gaseous and liquid targets by ultraviolet radiation. UV pump-XUV probe measurements in ethyl-iodide showcase the capabilities of the attosecond beamline.

Versatile multi-energy hard x-ray camera to study confined and unconfined fast electron dynamics and anisotropies (Invited).

A powerful and flexible hard x-ray (HXR) camera has been recently installed and tested on the WEST tokamak (CEA, France) in collaboration with the Princeton Plasma Physics Laboratory. The diagnostic is a pinhole camera fielded with a 2D pixel detector equipped with a 1mm thick CdTe sensor. The novelty of this diagnostic technique is the detector's capability of adjusting the threshold energy at the pixel level. This innovation provides great flexibility in the energy configuration, allowing simultaneous space, energy, and time resolved x-ray measurements. The novel camera has been used to measure the core radiation from non-Maxwellian (fast) electrons accelerated by Lower Hybrid (LH) waves and also the beam-target emission of tungsten in the divertor region produced by fast electron losses interacting with the target. In addition, anisotropic hard x-ray emission has been detected for the first time at the WEST core and edge plasma, with opposite toroidal intensity trends. Experimental vertical and toroidal HXR profiles have been successfully reproduced with the LH code LUKE.

Statistical Distribution of the Peak Frequency of ECH Waves in the Outer Magnetosphere From Magnetospheric Multiscale Satellite Observations

AbstractElectron cyclotron harmonic (ECH) waves are electrostatic emissions with frequencies between the harmonics of the electron gyrofrequencies. Their frequency properties provide clues for understanding their generation and are keys to evaluating their scattering efficiency. Based on Magnetospheric Multiscale satellite observations, we explored the statistical frequency properties of first‐harmonic band ECH waves in the outer magnetosphere. The frequencies at the peak power of ECH waves are found to be day‐night and dawn‐dusk asymmetries, with higher values in the regions from dawn to post‐noon, and these asymmetries are more evident during weaker geomagnetic activity. Furthermore, the frequencies at the peak power of ECH waves decrease gradually with increasing |MLAT| and are positively correlated with their amplitudes at each magnetic local time or |MLAT|. Information on the frequency properties of ECH waves presented in this study can be crucial for future modeling of their contributions to magnetospheric electron dynamics.

Gyrokinetic simulations of the kinetic electron effects on the electrostatic instabilities on the ITER baseline scenario

The linear and nonlinear simulations are carried out using the gyrokinetic code NLT for the electrostatic instabilities in the core region of a deuterium plasma based on the International Thermonuclear Experimental Reactor (ITER) baseline scenario. The kinetic electron effects on the linear frequency and nonlinear transport are studied by adopting the adiabatic electron model and the fully drift-kinetic electron model in the NLT code, respectively. The linear simulations focus on the dependence of linear frequency on the plasma parameters, such as the ion and electron temperature gradients , the density gradient and the ion–electron temperature ratio . Here, is the major radius, and and denote the electron and ion temperatures, respectively. is the gradient scale length, with denoting the density, the ion and electron temperatures, respectively. In the kinetic electron model, the ion temperature gradient (ITG) instability and the trapped electron mode (TEM) dominate in the small and large region, respectively, where is the poloidal wavenumber. The TEM-dominant region becomes wider by increasing (decreasing) ( ) or by decreasing . For the nominal parameters of the ITER baseline scenario, the maximum growth rate of dominant ITG instability in the kinetic electron model is about three times larger than that in the adiabatic electron model. The normalized linear frequency depends on the value of , rather than the value of or , in both the adiabatic and kinetic electron models. The nonlinear simulation results show that the ion heat diffusivity in the kinetic electron model is quite a lot larger than that in the adiabatic electron model, the radial structure is finer and the time oscillation is more rapid. In addition, the magnitude of the fluctuated potential at the saturated stage peaks in the ITG-dominated region, and contributions from the TEM (dominating in the higher region) to the nonlinear transport can be neglected. In the adiabatic electron model, the zonal radial electric field is found to be mainly driven by the turbulent energy flux, and the contribution of turbulent poloidal Reynolds stress is quite small due to the toroidal shielding effect. However, in the kinetic electron model, the turbulent energy flux is not strong enough to drive the zonal radial electric field in the nonlinear saturated stage. The kinetic electron effects on the mechanism of the turbulence-driven zonal radial electric field should be further investigated.

Simulating ultrafast transient absorption spectra from first principles using a time-dependent configuration interaction probe.

Transient absorption spectroscopy (TAS) is among the most common ultrafast photochemical experiments, but its interpretation remains challenging. In this work, we present an efficient and robust method for simulating TAS signals from first principles. Excited-state absorption and stimulated emission (SE) signals are computed using time-dependent complete active space configuration interaction (TD-CASCI) simulations, leveraging the robustness of time-domain simulation to minimize electronic structure failure. We demonstrate our approach by simulating the TAS signal of 1'-hydroxy-2'-acetonapthone (HAN) from ab initio multiple spawning nonadiabatic molecular dynamics simulations. Our results are compared to gas-phase TAS data recorded from both jet-cooled (T ∼ 40 K) and hot (∼403 K) molecules via cavity-enhanced TAS (CE-TAS). Decomposition of the computed spectrum allows us to assign a rise in the SEsignal to excited-state proton transfer and the ultimate decay of the signal to relaxation through a twisted conical intersection. The total cost of computing the observable signal (∼1700 graphics processing unit hours for ∼4ns of electron dynamics) was markedly less than that of performing the abinitio multiple spawning calculations used to compute the underlying nonadiabatic dynamics.