Electronic Relaxation Dynamics Research Articles

Influence of Aliphatic versus Aromatic Ligand Passivation on Intersystem Crossing in Au25(SR)18.

The electronic relaxation dynamics of gold monolayer protected clusters (MPCs) are influenced by the hydrocarbon structure of thiolate protecting ligands. Here, we present ligand-dependent electronic relaxation for a series of Au25(SR)18- (SR = SC8H9, SC6H13, SC12H25) MPCs using femtosecond time-resolved transient absorption spectroscopy. Relaxation pathways included a ligand-independent femtosecond internal conversion and a competing ligand-dependent picosecond intersystem crossing process. Intersystem crossing was accelerated for the aliphatic (SC6H13, SC12H25) thiolate MPCs compared to the aromatic (SC8H9) thiolate MPCs. Additionally, a 1.2 THz quadrupolar acoustic mode and a 2.4 THz breathing acoustic mode was identified in each cluster, which indicated that differences in ligand structure did not result in significant structural changes to the metal core of the MPCs. Considering that the difference in relaxation rates did not result from ligand-induced core deformation, the accelerated intersystem crossing was attributed to greater electron-vibrational coupling to Au-S vibrational modes. The results suggested that the organometallic semiring was less rigid for the aliphatic thiolate MPCs due to reduced steric effects, and in turn, increases in nonradiative decay rates were observed. Overall, these results imply that the protecting ligand structure can be used to modify carrier relaxation in MPCs.

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.

Hot carrier relaxation dynamics of an aza-covalent organic framework during photoexcitation: An insight from abinitio quantum dynamics.

In order to develop an efficient metal-free solar energy harvester, we herein performed the electronic structure calculation, followed by the hot carrier relaxation dynamics of two dimensional (2D) aza-covalent organic framework by time domain density functional calculations in conjunction with non-adiabatic molecular dynamics (NAMD) simulation. The electronic structure calculation shows that the aza-covalent organic framework (COF) is a direct bandgap semiconductor with acute charge separation and effective optical absorption in the UV-visible region. Our study of non-adiabatic molecular dynamics simulation predicts the sufficiently prolonged electron-hole recombination process (6.8 nanoseconds) and the comparatively faster electron (22.48ps) and hole relaxation (0.51ps) dynamics in this two-dimensional aza-COF. According to our theoretical analysis, strong electron-phonon coupling is responsible for the rapid charge relaxation, whereas the electron-hole recombination process is slowed down by relatively weak electron-phonon coupling, relatively lower non-adiabatic coupling, and quick decoherence time. We do hope that our results of NAMD simulation on exciton relaxation dynamics will be helpful for designing photovoltaic devices based on this two dimensional aza-COF.

Thickness-dependent electronic relaxation dynamics in solution-phase redox-exfoliated MoS2 heterostructures.

Electronic relaxation dynamics of solution-phase redox-exfoliated molybdenum disulfide (MoS2) monolayer and multilayer ensembles are described. MoS2 was exfoliated using polyoxometalate (POM) reductants. This process yields a colloidal heterostructure consisting of MoS2 2D sheet multilayers with surface-bound POM complexes. Using two-dimensional electronic spectroscopy, transient bleaching and photoinduced absorption signals were detected at excitation/detection energies of 1.82/1.87 and 1.82/1.80eV, respectively. Approximate 100-fs bandgap renormalization (BGR) and subsequent defect- and phonon-mediated relaxation on the picosecond timescale were resolved for several MoS2 thicknesses spanning from 1 to 2 L to ∼20 L. BGR rates were independent of sample thickness and slightly slower than observations for chemical vapor deposition-grown MoS2 monolayers. However, defect-mediated relaxation accelerated ∼10-fold with increased sample thicknesses. The relaxation rates increased from 0.33 ± 0.05 to 1.2 ± 0.1 and 3.1 ± 0.4ps-1 for 1-2 L, 3-4 L, and 20 L fractions. The thicknesses-dependent relaxation rates for POM-MoS2 heterostructures were modeled using a saturating exponential function that showed saturation at thirteen MoS2 layers. The results suggest that the increased POM surface coverage leads to larger defect density in the POM-MoS2 heterostructure. These are the first descriptions of the influence of sample thickness on electronic relaxation rates in solution-phase redox-exfoliated POM-MoS2 heterostructures. Outcomes of this work are expected to impact the development of solution-phase exfoliation of 2D metal-chalcogenide heterostructures.

Phototransformation of achiral metasurfaces into handedness-selectable transient chiral media

Chirality is a geometric property describing the lack of mirror symmetry. This unique feature enables photonic spin-selectivity in light-matter interaction, which is of great significance in stereochemistry, drug development, quantum optics, and optical polarization control. The versatile control of optical geometry renders optical metamaterials as an effective platform for engineered chiral properties at prescribed spectral regimes. Unfortunately, geometry-imposed restrictions only allow one circular polarization state of photons to effectively interact with chiral meta-structures. This limitation motivates the idea of discovering alternative techniques for dynamically reconfiguring the chiroptical responses of metamaterials in a fast and facile manner. Here, we demonstrate an approach that enables optical, sub-picosecond conversion of achiral meta-structures to transient chiral media in the visible regime with desired handedness upon the inhomogeneous generation of plasmonic hot electrons. As a proof of concept, we utilize linearly polarized laser pulse to demonstrate near-complete conversion of spin sensitivity in an achiral meta-platform-a functionality yet achieved in a non-mechanical fashion. Owing to the generation, diffusion, and relaxation dynamics of hot electrons, the demonstrated technique for all-optical creation of chirality is inherently fast, opening new avenues for ultrafast spectro-temporal construction of chiral platforms with on-demand spin-selectivity.

Electron-phonon coupling dictates electron mean free paths and negative thermal diffusion in metals

The spatiotemporal dynamics of the fundamental energy carriers in metals underpin the efficiency of a wide array of technologies. Although much progress in our understanding of the temporal response of electronic relaxation processes following an external field perturbation has been achieved, the spatial relaxation dynamics of electrons after excitation remains unclear. Here, we employ a scanning ultrafast microscopy with high spatial resolution to directly measure the mean free paths of electrons in different metals. We show that the strength of electron-phonon coupling not only dictates the mean free paths, but also controls a peculiar spatial shrinking of the electronic temperature profile immediately after the electrons have thermalized with the ‘colder’ lattice. More specifically, from our experimental tracking of the spatial relaxation profiles, a clear observation of an effective negative thermal diffusion is apparent for metals with weaker electron-phonon coupling, while for metals with stronger electron-phonon coupling, the negative thermal diffusion effect is not observable. Our spatiotemporal modeling based on the two-temperature approach provides evidence that although negative diffusion occurs universally for materials with two different species that have varying diffusivities and are thermodynamically coupled, effective negative diffusion is masked for cases with stronger coupling between the species.

Luminescent Radicals.

Organic radicals are attracting increasing interest as a new class of molecular emitters. They demonstrate electronic excitation and relaxation dynamics based on their doublet or higher multiplet spin states, which are different from those based on singlet-triplet manifolds of conventional closed-shell molecules. Recent studies have disclosed luminescence properties and excited state dynamics unique to radicals, such as highly efficient electron-photon conversion in OLEDs, NIR emission, magnetoluminescence, an absence of heavy atom effect, and spin-dependent and spin-selective dynamics. These are difficult or sometimes impossible to achieve with closed-shell luminophores. This review focuses on luminescent organic radicals as an emerging photofunctional molecular system, and introduces the material developments, fundamental properties including luminescence, and photofunctions. Materials covered in this review range from monoradicals, radical oligomers, and radical polymers to metal complexes with radical ligands demonstrating radical-involved emission. In addition to stable radicals, transiently formed radicals generated in situ by external stimuli are introduced. This review shows that luminescent organic radicals have great potential to expand the chemical and spin spaces of luminescent molecular materials and thus broaden their applicability to photofunctional systems.

Tensile Strain-Dependent Ultrafast Electron Transfer and Relaxation Dynamics in Flexible WSe2/MoS2 Heterostructures.

Understanding and controlling carrier dynamics in two-dimensional (2D) van der Waals heterostructures through strain are crucial for their flexible applications. Here, femtosecond transient absorption spectroscopy is employed to elucidate the interlayer electron transfer and relaxation dynamics under external tensile strains in a WSe2/MoS2 heterostructure. The results show that a modest ∼1% tensile strain can significantly alter the lifetimes of electron transfer and nonradiative electron-hole recombination by >30%. Ab initio non-adiabatic molecular dynamics simulations suggest that tensile strain weakens the electron-phonon coupling, thereby suppressing the transfer and recombination dynamics. Theoretical predictions indicate that strain-induced energy difference increases along the electron transfer path could contribute to the prolongation of the transfer lifetime. A subpicosecond decay process, related to hot-electron cooling, remains almost unaffected by strain. This study demonstrates the potential of tuning interlayer carrier dynamics through external strains, offering insights into flexible optoelectronic device design with 2D materials.

Electron–Phonon Relaxation Dynamics of Hot Electrons in Gold Nanoparticles Are Independent of Excitation Pathway

Electron–Phonon Relaxation Dynamics of Hot Electrons in Gold Nanoparticles Are Independent of Excitation Pathway

Ultrafast Electronic Relaxation Dynamics of Atomically Thin MoS2 Is Accelerated by Wrinkling.

Strain engineering is an attractive approach for tuning the local optoelectronic properties of transition metal dichalcogenides (TMDs). While strain has been shown to affect the nanosecond carrier recombination dynamics of TMDs, its influence on the sub-picosecond electronic relaxation dynamics is still unexplored. Here, we employ a combination of time-resolved photoemission electron microscopy (TR-PEEM) and nonadiabatic ab initio molecular dynamics (NAMD) to investigate the ultrafast dynamics of wrinkled multilayer (ML) MoS2 comprising 17 layers. Following 2.41 eV photoexcitation, electronic relaxation at the Γ valley occurs with a time constant of 97 ± 2 fs for wrinkled ML-MoS2 and 120 ± 2 fs for flat ML-MoS2. NAMD shows that wrinkling permits larger amplitude motions of MoS2 layers, relaxes electron-phonon coupling selection rules, perturbs chemical bonding, and increases the electronic density of states. As a result, the nonadiabatic coupling grows and electronic relaxation becomes faster compared to flat ML-MoS2. Our study suggests that the sub-picosecond electronic relaxation dynamics of TMDs is amenable to strain engineering and that applications which require long-lived hot carriers, such as hot-electron-driven light harvesting and photocatalysis, should employ wrinkle-free TMDs.

Modulation of Phonons and Excitons Due to Moiré Potentials in Twisted Bilayer of WSe2/MoSe2.

The application of two-dimensional materials has been expanded by introducing the twisted bilayer (TBL) system. However, the landscape of the interlayer interaction in hetero-TBLs has not yet been fully understood, while that in homo-TBLs has been extensively studied, with the dependence on the twist angle between the constituent layers. Here, we present detailed analyses on the interlayer interaction that depends on the twist angle in WSe2/MoSe2 hetero-TBL via Raman and photoluminescence studies combined with first-principles calculation. We observe interlayer vibrational modes, moiré phonons, and the interlayer excitonic states that evolve with the twist angle and identify different regimes with distinct characteristics of such features. Moreover, the interlayer excitons that appear strong in the hetero-TBLs with twist angles near 0° or 60° have different energies and photoluminescence excitation spectra for the two cases, which results from different electronic structures and carrier relaxation dynamics. These results would enable a better understanding of the interlayer interaction in hetero-TBLs.

Photoreduced graphene oxide recovers graphene hot electron cooling dynamics

Reduced graphene oxide (rGO) is a bulk-processable quasi-amorphous 2D material with broad spectral coverage and fast electronic response. rGO sheets are suspended in a polymer matrix and sequentially photoreduced while measuring the evolving optical spectra and ultrafast electron relaxation dynamics. Photoreduced rGO yields optical absorption spectra that fit with the same Fano lineshape parameters as monolayer graphene. With increasing photoreduction time, rGO transient absorption kinetics accelerate monotonically, reaching an optimal point that matches the hot electron cooling in graphene. All stages of rGO ultrafast kinetics are simulated with a hot-electron cooling model mediated by disorder-assisted supercollisions. While the rGO room temperature 0.31 ps$^{-1}$ electronic cooling rate matches monolayer graphene, subsequent photoreduction can rapidly increase the rate by ~10-12$\times$. Such accelerated supercollision rates imply a reduced mean-free scattering length caused by photoionized point-defects on the rGO sp$^2$ sub-lattice. For visible range excitations of rGO, photoreduction shows three increasing spectral peaks that match graphene quantum dot (GQD) transitions, while a broad peak from oxygenated defect edge states shrinks. These three confined GQD states donate their hot carriers to the graphene sub-lattice with a 0.17 ps rise-time that accelerates with photoreduction. Collectively, many desirable photophysical properties of 2D graphene are replicated through selectively reducing rGO scaffolded within a 3D bulk polymeric network.

Characterization of charge-carrier dynamics at the Bi2Se3/MgF2 interface by multiphoton pumped UV–Vis transient absorption spectroscopy

Separate relaxation dynamics of electrons and holes in experiments on optical pumping-probing of semiconductors is rarely observed due to their overlap. Here we report the separate relaxation dynamics of long-lived (∼200 μs) holes observed at room temperature in a 10 nm thick film of the 3D topological insulator (TI) Bi2Se3 coated with a 10 nm thick MgF2 layer using transient absorption spectroscopy in the UV–Vis region. The ultraslow hole dynamics was observed by applying resonant pumping of massless Dirac fermions and bound valence electrons in Bi2Se3 at a certain wavelength sufficient for their multiphoton photoemission and subsequent trapping at the Bi2Se3/MgF2 interface. The emerging deficit of electrons in the film makes it impossible for the remaining holes to recombine, thus causing their ultraslow dynamics measured at a specific probing wavelength. We also found an extremely long rise time (∼600 ps) for this ultraslow optical response, which is due to the large spin–orbit coupling splitting at the valence band maximum and the resulting intervalley scattering between the splitting components. The observed dynamics of long-lived holes is gradually suppressed with decreasing Bi2Se3 film thickness for the 2D TI Bi2Se3 (film thickness below 6 nm) due to the loss of resonance conditions for multiphoton photoemission caused by the gap opening at the Dirac surface state nodes. This behavior indicates that the dynamics of massive Dirac fermions predominantly determines the relaxation of photoexcited carriers for both the 2D topologically nontrivial and 2D topologically trivial insulator phases.

Ultrafast Laser Control of Antiferromagnetic-Ferrimagnetic Switching in Two-Dimensional Ferromagnetic Semiconductor Heterostructures.

Realizing ultrafast control of magnetization switching is of crucial importance for information processing and recording technology. Here, we explore the laser-induced spin electron excitation and relaxation dynamics processes of CrCl3/CrBr3 heterostructures with antiparallel (AP) and parallel (P) systems. Although an ultrafast demagnetization of CrCl3 and CrBr3 layers occurs in both AP and P systems, the overall magnetic order of the heterostructure remains unchanged due to the laser-induced equivalent interlayer spin electron excitation. More crucially, the interlayer magnetic order switches from antiferromagnetic (AFM) to ferrimagnetic (FiM) in the AP system once the laser pulse disappears. The microscopic mechanism underpinning this magnetization switching is dominated by the asymmetrical interlayer charge transfer combined with a spin-flip, which breaks the interlayer AFM symmetry and ultimately results in an inequivalent shift in the moment between two FM layers. Our study opens up a new idea for ultrafast laser control of magnetization switching in two-dimensional opto-spintronic devices.

Ultrafast Electronic Relaxation in Aqueous [Fe(bpy)3]2+: A Surface Hopping Study.

Trajectory surface hopping simulations are performed to better understand the electronic relaxation dynamics of [Fe(bpy)3]2+ in aqueous solution. Specifically, the ultrafast relaxation from the photoexcited singlet metal-to-ligand charge-transfer (MLCT) to the metastable quintet metal-centered (MC) states is simulated through the surface hopping method, where the MLCT and MC states of [Fe(bpy)3]2+ in aqueous solution are computed by using a model electronic Hamiltonian developed previously. As a result, most of the trajectories are interpreted to show the sequential relaxation pathways via the triplet MC states, though some are the direct pathway from MLCT to the quintet MC states. Even though the triplet MC states are involved in the relaxation, the population transfer to the singlet MC ground state is very small, and the population of the quintet MC states reaches more than ∼96%, reasonably consistent with the unity quantum efficiency discussed experimentally.

Distortion Correction of Low-Energy Photoelectron Spectra of Liquids Using Spectroscopic Data for Solvated Electrons.

Time-resolved photoelectron spectroscopy (TRPES) enables real-time observation of ultrafast electronic dynamics in solutions. When extreme ultraviolet (EUV) probe pulses are employed, they can ionize solutes from all electronic states involved in the dynamics. However, EUV pulses also produce a strong ionization signal from a solvent that is typically 6 orders of magnitude greater than the pump-probe photoelectron signal of solutes. Alternatively, UV probe pulses enable highly sensitive and selective observation of photoexcited solutes because typical solvents such as water are transparent to UV radiation. An obstacle in such UV-TRPES measurements is spectral distortion caused by electron scattering and a yet to be identified mechanism in liquids. We have previously proposed the spectral retrieval (SR) method as an a posteriori approach to removing the distortion and overcoming this difficulty in UV-TRPES; however, its accuracy has not yet been verified by comparison with EUV-TRPES results. In the present study, we perform EUV-TRPES for charge transfer reactions in water, methanol, and ethanol, and verify SR analysis of UV-TRPES. We also estimate a previously undetermined energy-dependent intensity factor and expand the basis sets for SR analysis. The refined SR method is employed for reanalyzing the UV-TRPES data for the formation and relaxation dynamics of solvated electrons in various systems. The electron binding energy distributions for solvated electrons in liquid water, methanol, and ethanol are confirmed to be Gaussian centered at 3.78, 3.39, and 3.25 eV, respectively, in agreement with Nishitani et al. [ Sci. Adv. 2019, 5(8), eaaw6896]. An effective energy gap between the conduction band and the vacuum level at the gas-liquid interface is estimated to be 0.2 eV for liquid water and 0.1 eV for methanol and ethanol.

Observation of a transient intermediate in the ultrafast relaxation dynamics of the excess electron in strong-field-ionized liquid water

A unified picture of the electronic relaxation dynamics of ionized liquid water has remained elusive despite decades of study. Here, we employ sub-two-cycle visible to short-wave infrared pump-probe spectroscopy and ab initio nonadiabatic molecular dynamics simulations to reveal that the excess electron injected into the conduction band (CB) of ionized liquid water undergoes sequential relaxation to the hydrated electron s ground state via an intermediate state, identified as the elusive p excited state. The measured CB and p-electron lifetimes are 0.26 ± 0.02 ps and 62 ± 10 fs, respectively. Ab initio quantum dynamics yield similar lifetimes and furthermore reveal vibrational modes that participate in the different stages of electronic relaxation, with initial relaxation within the dense CB manifold coupled to hindered translational motions whereas subsequent p-to-s relaxation facilitated by librational and even intramolecular bending modes of water. Finally, energetic considerations suggest that a hitherto unobserved trap state resides ~0.3-eV below the CB edge of liquid water. Our results provide a detailed atomistic picture of the electronic relaxation dynamics of ionized liquid water with unprecedented time resolution.

Nonadiabatic Molecular Dynamics with Extended Density Functional Tight-Binding: Application to Nanocrystals and Periodic Solids.

In this work, we report a new methodology for nonadiabatic molecular dynamics calculations within the extended tight-binding (xTB) framework. We demonstrate the applicability of the developed approach to finite and periodic systems with thousands of atoms by modeling "hot" electron relaxation dynamics in silicon nanocrystals and electron-hole recombination in both a graphitic carbon nitride monolayer and a titanium-based metal-organic framework (MOF). This work reports the nonadiabatic dynamic simulations in the largest Si nanocrystals studied so far by the xTB framework, with diameters up to 3.5 nm. For silicon nanocrystals, we find a non-monotonic dependence of "hot" electron relaxation rates on the nanocrystal size, in agreement with available experimental reports. We rationalize this relationship by a combination of decreasing nonadiabatic couplings related to system size and the increase of available coherent transfer pathways in systems with higher densities of states. We emphasize the importance of proper treatment of coherences for obtaining such non-monotonic dependences. We characterize the electron-hole recombination dynamics in the graphitic carbon nitride monolayer and the Ti-containing MOF. We demonstrate the importance of spin-adaptation and proper sampling of surface hopping trajectories in modeling such processes. We also assess several trajectory surface hopping schemes and highlight their distinct qualitative behavior in modeling the excited-state dynamics in superexchange-like models depending on how they handle coherences between nearly parallel states.

Enhancement of Plasmon-Induced Photoelectrocatalytic Water Oxidation over Au/TiO2 with Lithium Intercalation.

Plasmon-induced chemical reaction is an emerging field but its development faces huge challenges because of low quantum efficiency. Herein, we report that the solar energy conversion efficiency of Au/TiO2 in plasmon-induced water oxidation is greatly enhanced by intercalating Li+ into TiO2 . An incident photon-to-current efficiency as high as 2.0 %@520 nm is achieved by Au/Li0.2 TiO2 in photoelectrocatalytic water oxidation, realizing a 33-fold enhancement in photocurrent density compared with Au/TiO2 . The superior photoelectrocatalytic performance is mainly ascribed to the enhanced electric conductivity and higher catalytic activity of Li0.2 TiO2 . Furthermore, the ultrafast transient absorption spectroscopy suggests that lithium intercalation into TiO2 could change the dynamics of hot electron relaxation in Au nanoparticles. This work demonstrates that intercalation of alkaline ions into semiconductors can promote the charge separation efficiency of the plasmonic effect of Au/TiO2 .

Enhancement of Plasmon‐Induced Photoelectrocatalytic Water Oxidation over Au/TiO2 with Lithium Intercalation

AbstractPlasmon‐induced chemical reaction is an emerging field but its development faces huge challenges because of low quantum efficiency. Herein, we report that the solar energy conversion efficiency of Au/TiO2 in plasmon‐induced water oxidation is greatly enhanced by intercalating Li+ into TiO2. An incident photon‐to‐current efficiency as high as 2.0 %@520 nm is achieved by Au/Li0.2TiO2 in photoelectrocatalytic water oxidation, realizing a 33‐fold enhancement in photocurrent density compared with Au/TiO2. The superior photoelectrocatalytic performance is mainly ascribed to the enhanced electric conductivity and higher catalytic activity of Li0.2TiO2. Furthermore, the ultrafast transient absorption spectroscopy suggests that lithium intercalation into TiO2 could change the dynamics of hot electron relaxation in Au nanoparticles. This work demonstrates that intercalation of alkaline ions into semiconductors can promote the charge separation efficiency of the plasmonic effect of Au/TiO2.