Subpicosecond Dynamics Research Articles

Subpicosecond Dynamics of Rydberg Excitons Produced from Ultraviolet Excitation of Neutral Cuprite (Cu2O)n Clusters, n < 13.

The ultrafast dynamics of subnanometer neutral cuprite clusters (Cu2O)n, n < 13, are examined with pump probe spectroscopy. Upon absorption of an ultraviolet (400 nm) photon, all clusters exhibit a subpicosecond lifetime that we attribute to carrier recombination. Density functional theory (DFT) shows a change in the structural motif between small planar clusters and three-dimensional structures at n = 4. This transition is accompanied by a change in the excited state relaxation behavior, marking the onset for which lifetimes increase gradually with size. Time-dependent DFT calculations show that the excited state lifetimes align with calculated topological parameters and charge carrier delocalization associated with the formation of Rydberg excitons. Terminal Cu atoms are found to be important for the production of Rydberg excitons at the lowest optically allowed excited state. Upon excitation, the electron resides on terminal Cu atoms and the hole becomes delocalized across the remainder of the cluster.

(Sub-)Picosecond Surface Correlations of Femtosecond Laser Excited Al-Coated Multilayers Observed by Grazing-Incidence X-ray Scattering.

Femtosecond high-intensity laser pulses at intensities surpassing 1014 W/cm2 can generate a diverse range of functional surface nanostructures. Achieving precise control over the production of these functional structures necessitates a thorough understanding of the surface morphology dynamics with nanometer-scale spatial resolution and picosecond-scale temporal resolution. In this study, we show that single XFEL pulses can elucidate structural changes on surfaces induced by laser-generated plasmas using grazing-incidence small-angle X-ray scattering (GISAXS). Using aluminium-coated multilayer samples we distinguish between sub-picosecond (ps) surface morphology dynamics and subsequent multi-ps subsurface density dynamics with nanometer-depth sensitivity. The observed subsurface density dynamics serve to validate advanced simulation models representing matter under extreme conditions. Our findings promise to open new avenues for laser material-nanoprocessing and high-energy-density science.

MANUSCRIPT Local Crowd, Local Probe: Strengths and Drawbacks of Azidohomoalanine as a Site-Specific Crowding Probe.

Every residue on a protein can be characterized by its interaction with water, in lack or in excess, as water is the matrix of biological systems. Infrared spectroscopy and the implementation of local azidohomoalanine (AHA) probes allow us to move beyond an ensemble or surface-driven conceptualization of water behavior and toward a granular, site-specific picture. In this paper, we examined the role of crowding in modulating both global and local behavior on the β-hairpin, TrpZip2 using a combination of Fourier-transform infrared spectroscopy (FTIR) spectroscopy, two-dimensional infrared (2D IR) spectroscopy, and molecular dynamics simulations. We found that, at the amino acid level, crowding drove dehydration of both sheet and turn peptide sites as well as free AHA. However, the subpicosecond dynamics showed highly individualized responses based on the local environment. Interestingly, while steady-state FTIR measurements revealed similar responses at the amino-acid level to hard versus soft crowding (dehydration), we found that PEG and glucose had opposite stabilizing and destabilizing effects on the protein secondary structure, emphasizing an important distinction in understanding the impact of crowding on protein structure as well as the role of crowding across length scales.

Optical probing of ultrafast laser-induced solid-to-overdense-plasma transitions

Understanding the solid target dynamics resulting from the interaction with an ultrashort laser pulse is a challenging fundamental multi-physics problem involving atomic and solid-state physics, plasma physics, and laser physics. Knowledge of the initial interplay of the underlying processes is essential to many applications ranging from low-power laser regimes like laser-induced ablation to high-power laser regimes like laser-driven ion acceleration. Accessing the properties of the so-called pre-plasma formed as the laser pulse’s rising edge ionizes the target is complicated from the theoretical and experimental point of view, and many aspects of this laser-induced transition from solid to overdense plasma over picosecond timescales are still open questions. On the one hand, laser-driven ion acceleration requires precise control of the pre-plasma because the efficiency of the acceleration process crucially depends on the target properties at the arrival of the relativistic intensity peak of the pulse. On the other hand, efficient laser ablation requires, for example, preventing the so-called “plasma shielding”. By capturing the dynamics of the initial stage of the interaction, we report on a detailed visualization of the pre-plasma formation and evolution. Nanometer-thin diamond-like carbon foils are shown to transition from solid to plasma during the laser rising edge with intensities < 1016 W/cm². Single-shot near-infrared probe transmission measurements evidence sub-picosecond dynamics of an expanding plasma with densities above 1023 cm−3 (about 100 times the critical plasma density). The complementarity of a solid-state interaction model and kinetic plasma description provides deep insight into the interplay of initial ionization, collisions, and expansion.

Two-photon Absorption and Photoionization of a Bacterial Phytochrome

Phytochromes constitute a family of photosensory proteins that are utilized by various organisms to regulate several physiological processes. Phytochromes bind a bilin pigment that switches its isomeric state upon absorption of red or far-red photons, resulting in protein conformational changes that are sensed by the organism. Previously, the ultrafast dynamics in bacterial phytochrome was resolved to atomic resolution by time-resolved serial femtosecond X-ray diffraction (TR-SFX), showing extensive changes in its molecular conformation at 1 picosecond delay time. However, the large excitation fluence of mJ/mm2 used in TR-SFX questions the validity of the observed dynamics. In this work, we present an excitation-dependent ultrafast transient absorption study to test the response of a related bacterial phytochrome to excitation fluence. We observe excitation power-dependent sub-picosecond dynamics, assigned to the population of high-lying excited state Sn through resonantly enhanced two-photon absorption, followed by rapid internal conversion to the low-lying S1 state. Inspection of the long-lived spectrum under high fluence shows that in addition to the primary intermediate Lumi-R, spectroscopic signatures of solvated electrons and ionized chromophore radicals are observed. Supported by numerical modelling, we propose that under excitation fluences of tens of μJ/mm2 and higher, bacterial phytochrome partly undergoes photoionization from the Sn state in competition with internal conversion to the S1 state in 300 fs. We suggest that the extensive structural changes of related, shorter bacterial phytochrome, lacking the PHY domain, resolved from TR-SFX may have been affected by the ionized species. We propose approaches to minimize the two-photon absorption process by tuning the excitation spectrum away from the S1 absorption or using phytochromes exhibiting minimized or shifted S1 absorption.

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.

Ab Initio Simulation of the Ultrafast Circular Dichroism Spectrum of Provitamin D Ring-Opening.

We present a method to simulate ultrafast pump-probe time-resolved circular dichroism (TRCD) spectra based on time-dependent density functional theory trajectory surface hopping. The method is applied to simulate the TRCD spectrum along the photoinduced ring-opening of provitamin D. Simulations reveal that the initial decay of the signal is due to excited state relaxation, forming the rotationally flexible previtamin D. We further show that oscillations in the experimental TRCD spectrum arise from isomerizations between previtamin D rotamers with different chirality, which are associated with the helical conformation of the triene unit. We give a detailed description of the formation dynamics of different rotamers, playing a key role in the natural regulation of vitamin D photosynthesis. Going beyond the sole extraction of decay rates, simulations greatly increase the amount of information that can be retrieved from ultrafast TRCD, making it a sensitive tool to unravel details in the subpicosecond dynamics of photoinduced chirality changes.

Sub-Picosecond Carrier Dynamics Explored using Automated High-Throughput Studies of Doping Inhomogeneity within a Bayesian Framework.

Bottom-up production of semiconductor nanomaterials is often accompanied by inhomogeneity resulting in a spread in electronic properties which may be influenced by the nanoparticle geometry, crystal quality, stoichiometry, or doping. Using photoluminescence spectroscopy of a population of more than 11 000 individual zinc-doped gallium arsenide nanowires, inhomogeneity is revealed in, and correlation between doping and nanowire diameter by use of a Bayesian statistical approach. Recombination of hot-carriers is shown to be responsible for the photoluminescence lineshape; by exploiting lifetime variation across the population, hot-carrier dynamics is revealed at the sub-picosecond timescale showing interband electronic dynamics. High-throughput spectroscopy together with a Bayesian approach are shown to provide unique insight in an inhomogeneous nanomaterial population, and can reveal electronic dynamics otherwise requiring complex pump-probe experiments in highly non-equilibrium conditions.

Eigenmode analysis of the multiple temperature model: spectrum properties, hierarchical structures, and temperature inversion

Recent developments of ultrafast laser pulse techniques enable us to study the subpicosecond scale dynamics out of thermal equilibrium. Multiple temperature models (MTMs) are frequently used to describe such dynamics where the total system is divided into subsystems each of which is in local thermal equilibrium. Typical examples include the electron-lattice two temperature model and electron-spin-phonon three temperature model. We present the exact analytical solutions of linear MTM, based on the Fourier series expansion and the Green’s function method. We then discuss their properties for the case of the two and three temperature models. We show that the general solution of MTM is expressed as a linear combinations of a spatially uniform, single-temperature stationary mode and the other non-oscillatory, decaying “eigenmodes” characterized by different wave vectors and well-defined mode lifetimes. The eigenmode picture enables us to explore the hierarchical structure of models with respect to space, time and the coupling parameter. Excitation by source term is included by the Green’s function method. As an example, we derive an analytical solution for a Gaussian type source term. We report a phenomenon “temperature inversion” where the lattice temperature exceeds electron’s temperature for ns time scale. Furthermore, we show how physical requirements such as energy conservation and equilibration are realized in the general linear MTM in terms of the eigenmode picture.

Direct Observation of Ultrafast Lattice Distortions during Exciton-Polaron Formation in Lead Halide Perovskite Nanocrystals.

The microscopic origin of slow hot-carrier cooling in lead halide perovskites remains debated and has direct implications for applications. Slow hot-carrier cooling of several picoseconds has been attributed to either polaron formation or a hot-phonon bottleneck effect at high excited carrier densities (>1018 cm-3). These effects cannot be unambiguously disentangled with optical experiments alone. However, they can be distinguished by direct observations of ultrafast lattice dynamics, as these effects are expected to create qualitatively distinct fingerprints. To this end, we employ femtosecond electron diffraction and directly measure the sub-picosecond lattice dynamics of weakly confined CsPbBr3 nanocrystals following above-gap photoexcitation. While we do not observe signatures of a hot-phonon bottleneck lasting several picoseconds, the data reveal a light-induced structural distortion appearing on a time scale varying between 380 and 1200 fs depending on the excitation fluence. We attribute these dynamics to the effect of exciton-polarons on the lattice and the slower dynamics at high fluences to slower sub-picosecond hot-carrier cooling, which slows down the establishment of the exciton-polaron population. Further analysis and simulations show that the distortion is consistent with motions of the [PbBr3]- octahedral ionic cage, and closest agreement with the data is obtained for Pb-Br bond lengthening. Our work demonstrates how direct studies of lattice dynamics on the sub-picosecond time scale can discriminate between competing scenarios proposed in the literature to explain the origin of slow hot-carrier cooling in lead halide perovskites.

Quadrupolar 23Na+ NMR relaxation as a probe of subpicosecond collective dynamics in aqueous electrolyte solutions

Nuclear magnetic resonance relaxometry represents a powerful tool for extracting dynamic information. Yet, obtaining links to molecular motion is challenging for many ions that relax through the quadrupolar mechanism, which is mediated by electric field gradient fluctuations and lacks a detailed microscopic description. For sodium ions in aqueous electrolytes, we combine ab initio calculations to account for electron cloud effects with classical molecular dynamics to sample long-time fluctuations, and obtain relaxation rates in good agreement with experiments over broad concentration and temperature ranges. We demonstrate that quadrupolar nuclear relaxation is sensitive to subpicosecond dynamics not captured by previous models based on water reorientation or cluster rotation. While ions affect the overall water retardation, experimental trends are mainly explained by dynamics in the first two solvation shells of sodium, which contain mostly water. This work thus paves the way to the quantitative understanding of quadrupolar relaxation in electrolyte and bioelectrolyte systems.

Polarization-dependent subpicosecond demagnetization in iron garnets

Controlling the magnetization dynamics at the fastest speed is a major issue of fundamental condensed matter physics and its applications for data storage and processing technologies. It requires a deep understanding of the interactions between the degrees of freedom in solids, such as spin, electron, and lattice as well as their responses to external stimuli. In this paper, we systematically investigate the fluence dependence of ultrafast magnetization dynamics induced by below-bandgap ultrashort laser pulses in the ferrimagnetic insulators ${\mathrm{Bi}}_{x}{\mathrm{Y}}_{3\ensuremath{-}x}{\mathrm{Fe}}_{5}{\mathrm{O}}_{12}$ with $1\ensuremath{\le}{x}_{\mathrm{Bi}}\ensuremath{\le}3$. We demonstrate subpicosecond demagnetization dynamics in this material followed by a very slow remagnetization process. We prove that this demagnetization results from an ultrafast heating of iron garnets by two-photon absorption (TPA), suggesting a phonon-magnon thermalization time of $\ensuremath{\le}0.6$ ps. We explain the slow remagnetization timescale by the low phonon heat conductivity in garnets. Additionally, we show that the amplitudes of the demagnetization, optical change, and lattice strain can be manipulated by changing the ellipticity of the pump pulses. We explain this phenomenon considering the TPA circular dichroism. These findings open exciting prospects for ultrafast manipulation of spin, charge, and lattice dynamics in magnetic insulators by ultrafast nonlinear optics.

Wave mixing efficiency in InAs/GaAs semiconductor quantum dot optical amplifiers and lasers

The nonlinear features of both semiconductor optical amplifiers (SOAs) and semiconductor lasers, which are made from the same InAs/GaAs quantum dot (QD) wafers, are investigated in detail. By employing pump-probe driven four-wave mixing as an experimental tool, the wave conversion process shows notably different profiles for the two types of devices. Due to the contributions of ultrafast, sub-picosecond mechanisms, such as carrier heating and spectral hole burning, the pump-probe frequency can be easily tuned to the THz range. SOAs generally benefit more from sub-picosecond carrier dynamics, hence exhibiting a higher conversion efficiency (CE) in the THz range, compared to their laser diode counterparts. The discrepancy even exceeds 10 dB. In addition, laser experiments yield some differences from the amplifier ones, hence leading to a higher nonlinear CE at small detuning ranges. These results strongly improve our insight into the fundamental nonlinear properties of InAs/GaAs QD material, and contribute to the conception of novel devices for future on-chip applications in all-optical communication networks, such as signal wavelength conversion, mode-locking, and optical frequency comb generation.

Impact of gigahertz and terahertz transport regimes on spin propagation and conversion in the antiferromagnet IrMn

Control over spin transport in antiferromagnetic systems is essential for future spintronic applications with operational speeds extending to ultrafast time scales. Here, we study the transition from the gigahertz (GHz) to terahertz (THz) regime of spin transport and spin-to-charge current conversion (S2C) in the prototypical antiferromagnet IrMn by employing spin pumping and THz spectroscopy techniques. We reveal a factor of 4 shorter characteristic propagation lengths of the spin current at THz frequencies (∼0.5 nm) as compared to GHz experiments (∼2 nm). This observation may be attributed to different transport regimes. The conclusion is supported by extraction of sub-picosecond temporal dynamics of the THz spin current. We identify no relevant impact of the magnetic order parameter on S2C signals and no scalable magnonic transport in THz experiments. A significant role of the S2C originating from interfaces between IrMn and magnetic or non-magnetic metals is observed, which is much more pronounced in the THz regime and opens the door for optimization of the spin control at ultrafast time scales.

Photocurrent-Detected 2D Electronic Spectroscopy Reveals Ultrafast Hole Transfer in Operating PM6/Y6 Organic Solar Cells.

The performance of nonfullerene-acceptor-(NFA)-based organic solar cells is rapidly approaching the efficiency of inorganic cells. The chemical versatility of NFAs extends the light-harvesting range to the infrared, while preserving a considerably high open-circuit-voltage, crucial to achieve power-conversion efficiencies >17%. Such low voltage losses in the charge separation process have been attributed to a low-driving-force and efficient exciton dissociation. Here, we address the nature of the subpicosecond dynamics of electron/hole transfer in PM6/Y6 solar cells. While previous reports focused on active layers only, we developed a photocurrent-detected two-dimensional spectroscopy to follow the charge transfer in fully operating devices. Our measurements reveal an efficient hole-transfer from the Y6-acceptor to the PM6-donor on the subpicosecond time scale. On the contrary, at the same time scale, no electron-transfer is seen from the donor to the acceptor. These findings, putting ultrafast spectroscopy in action on operating optoelectronic devices, provide insight for further enhancing NFA solar cell performance.

On the existence of soliton-like collective modes in liquid water at the viscoelastic crossover

The problem of large-density variations in supercooled and ambient water has been widely discussed in the past years. Recent studies have indicated the possibility of nanometer-sized density variations on the subpicosecond and picosecond time scales. The nature of fluctuating density heterogeneities remains a highly debated issue. In the present work, we address the problem of possible association of such density variations with the dynamics of terahertz longitudinal acoustic-like modes in liquid water. Our study is based on the fact that the subpicosecond dynamics of liquid water are essentially governed by the structural relaxation. Using a mode coupling theory approach, we found that for typical values of parameters of liquid water, the dynamic mechanism coming from the combination of the structural relaxation process and the finiteness of the amplitude of terahertz longitudinal acoustic-like mode gives rise to a soliton-like collective mode on a temperature-dependent nanometer length scale. The characteristics of this mode are consistent with the estimates of the amplitudes and temperature-dependent correlation lengths of density fluctuations in liquid water obtained in experiments and simulations. Thus, the fully dynamic mechanism could contribute to the formation and dynamics of fluctuating density heterogeneities. The soliton-like collective excitations suggested by our analysis may be relevant to different phenomena connected with supercooled water and can be expected to be associated with some ultrafast biological processes.

Singlet Fission Dynamics in Tetracene Single Crystals Probed by Polarization-Dependent Two-Dimensional Electronic Spectroscopy.

The exact mechanism of endothermic singlet fission in crystalline polyacene remains to be clarified. It has been elusive whether the excess energy of vibrational hot states and the upper branch of Davydov splitting is important for the energy compensation. Here, we probe the excited-state specified singlet fission dynamics in tetracene single crystals by polarization-dependent two-dimensional electronic spectroscopy (2DES). While a major spectral transfer with a characteristic lifetime of 86 ps is observed to be largely independent of the excitation energy due to formation of the spatially separated triplet pairs (1(T···T)), the excitation-energy dependent subpicosecond dynamics show marked differences for different states probed, implying the possible involvement of a coherently formed triplet pair state (1(TT)). Analysis of coherent vibrational modes suggests the coupling to high energy modes may offset the energy difference between singlet and triplet pair states. Moreover, the beating map of the low frequency mode indicates a vibrational hot state violating the aggregation behavior of Davydov exciton, which can be explained as a resonance of the 1(TT) state. These results suggest that the coherent vibronic mixing between local excitation and triplet pair states is essential for the singlet fission dynamics in molecule aggregates.

Sub-picosecond thermalization dynamics in condensation of strongly coupled lattice plasmons

Bosonic condensates offer exciting prospects for studies of non-equilibrium quantum dynamics. Understanding the dynamics is particularly challenging in the sub-picosecond timescales typical for room temperature luminous driven-dissipative condensates. Here we combine a lattice of plasmonic nanoparticles with dye molecule solution at the strong coupling regime, and pump the molecules optically. The emitted light reveals three distinct regimes: one-dimensional lasing, incomplete stimulated thermalization, and two-dimensional multimode condensation. The condensate is achieved by matching the thermalization rate with the lattice size and occurs only for pump pulse durations below a critical value. Our results give access to control and monitoring of thermalization processes and condensate formation at sub-picosecond timescale.

Sub-picosecond electron dynamics in polycrystalline diamond films

Polycrystalline diamond, as a composite material, primarily consists of sp3 and sp2 hybridized carbon phases in different ratio. The amount of grain boundaries, sp2 non-diamond carbon phase and other defects and impurities play a crucial role in relaxation and recombination of photo-excited charge carriers in diamond films. The transient transmission measurements are performed using non-degenerate pump and probe technique using few-cycle laser pulses with temporal resolution of ~15 fs. We show that the initial processes occurring after interaction of light with diamond membranes are sensitive to the sp3/sp2 ratio phases. We propose a simple microscopic model of electron relaxation via sub-gap energy levels caused by surface states, sp2 carbon phase and defects of the crystal lattice of diamond grains.

Competing ultrafast photoinduced electron transfer and intersystem crossing of [Re(CO)_3(Dmp)(His124)(Trp122)]^+ in Pseudomonas aeruginosa azurin: a nonadiabatic dynamics study

We present a computational study of sub-picosecond nonadiabatic dynamics in a rhenium complex coupled electronically to a tryptophan (Trp) side chain of Pseudomonas aeruginosa azurin, a prototypical protein used in the study of electron transfer in proteins. To gain a comprehensive understanding of the photoinduced processes in this system, we have carried out vertical excitation calculations at the TDDFT level of theory as well as nonadiabatic dynamics simulations using the surface hopping including arbitrary couplings (SHARC) method coupled to potential energy surfaces represented with a linear vibronic coupling model. The results show that the initial photoexcitation populates both singlet metal-to-ligand charge transfer (MLCT) and singlet charge-separated (CS) states, where in the latter an electron was transferred from the Trp amino acid to the complex. Subsequently, a complex mechanism of simultaneous intersystem crossing and electron transfer leads to the sub-picosecond population of triplet MLCT and triplet CS states. These results confirm the assignment of the sub-ps time constants of previous experimental studies and constitute the first computational evidence for the ultrafast formation of the charge-separated states in Re-sensitized azurin.