Ultrafast Time Scale Research Articles

Strong Nonlinear Optical Response and Transient Symmetry Switch in Type‐II Weyl Semimetal β‐WP2

AbstractThe topological Weyl semimetals (WSMs) with peculiar band structures exhibit novel nonlinear optical enhancement phenomena, even for light at optical wavelengths. While many intriguing nonlinear optical effects are constantly uncovered in type‐I WSMs, few experimental works focuse on basic nonlinear optical properties in type‐II WSMs. Here a static and time‐resolved second harmonic generation (SHG) is performed on the 3D type‐II WSM candidate β‐WP2. Although β‐WP2 exhibits extremely high conductivity and a high carrier density (≈1021 cm−3), the SHG is unscreened by conduction electrons, and a rather strong SHG response is observed, comparing with non‐topological polar metals. Additionally, the time‐resolved SHG experiment traces ultrafast symmetry switch and reveals that polar metal β‐WP2 tends to form an inversion symmetric metastable state after photo‐excitation. Intense femtosecond laser pulse can optically drive symmetry switch and tune nonlinear optical response on ultrafast timescales although the interlayer coupling of β‐WP2 is very strong. These findings are illuminating for the polar metal nonlinear optics and provide a new perspective for future ultrafast topological optoelectronic devices.

Multiparticle Cumulant Mapping for Coulomb Explosion Imaging.

We extend covariance velocity map ion imaging to four particles, establishing cumulant mapping and allowing for measurements that provide insights usually associated with coincidence detection, but at much higher count rates. Without correction, a fourfold covariance analysis is contaminated by the pairwise correlations of uncorrelated events, but we have addressed this with the calculation of a full cumulant, which subtracts pairwise correlations. We demonstrate the approach on the four-body breakup of formaldehyde following strong field multiple ionization in few-cycle laser pulses. We compare Coulomb explosion imaging for two different pulse durations (30 and 6fs), highlighting the dynamics that can take place on ultrafast timescales. These results have important implications for Coulomb explosion imaging as a tool for studying ultrafast structural changes in molecules, a capability that is especially desirable for high-count-rate x-ray free-electron laser experiments.

Nonlinear field-control of terahertz waves in random media for spatiotemporal focusing.

Controlling the transmission of broadband optical pulses in scattering media is a critical open challenge in photonics. To date, wavefront shaping techniques at optical frequencies have been successfully applied to control the spatial properties of multiple-scattered light. However, a fundamental restriction in achieving an equivalent degree of control over the temporal properties of a broadband pulse is the limited availability of experimental techniques to detect the coherent properties (i.e., the spectral amplitude and absolute phase) of the transmitted field. Terahertz experimental frameworks, on the contrary, enable measuring the field dynamics of broadband pulses at ultrafast (sub-cycle) time scales directly. In this work, we provide a theoretical/numerical demonstration that, within this context, complex scattering can be used to achieve spatio-temporal control of instantaneous fields and manipulate the temporal properties of single-cycle pulses by solely acting on spatial degrees of freedom of the illuminating field. As direct application scenarios, we demonstrate spatio-temporal focusing, chirp compensation, and control of the carrier-envelope-phase (CEP) of a CP-stable, transform-limited THz pulse.

Dissecting the Ultrafast Stepwise Bidirectional Proton Relay in a Blue-Light Photoreceptor.

Proton relays through H-bond networks are essential in realizing the functionality of protein machines such as in photosynthesis and photoreceptors. It has been challenging to dissect the rates and energetics of individual proton-transfer steps during the proton relay. Here, we have designed a proton rocking blue light using a flavin (BLUF) domain with the flavin mononucleotide (FMN)-glutamic acid (E)-tryptophan (W) triad and have resolved the four individual proton-transfer steps kinetically using ultrafast spectroscopy. We have found that after the photo-induced charge separation forming FMN·-/E-COOH/WH·+, the proton first rapidly jumps from the bridging E-COOH to FMN- (τfPT2 = 3.8 ps; KIE = 1.0), followed by a second proton transfer from WH·+ to E-COO- (τfPT1 = 336 ps; KIE = 2.6) which immediately rocks back to W· (τrPT1 = 85 ps; KIE = 6.7), followed by a proton return from FMNH· to E-COO- (τrPT2 = 34 ps; KIE = 3.3) with the final charge recombination between FMN·- and WH·+ to close the reaction cycle. Our results revisited the Grotthuss mechanism on the ultrafast timescale using the BLUF domain as a paradigm protein.

Rational design of ultrafast PpcA-Ru(bpy)3 complexes.

Converting light energy into its electrochemical equivalent requires precise control and fine-tuning of relevant kinetic and thermodynamic parameters of electron transfer (ET) steps. A particularly big challenge for artificial photosynthesis is to create the primary charge separation on the ultrafast (sub-nanosecond) time scale, as slower reactions are likely to require precious metal photosensitizers and produce significant amounts of reactive oxygen species. However, the structural requirements for ultrafast ET are poorly understood. The previous work from our lab has demonstrated that ET rates do not strictly depend on the distances. Similarly, we have demonstrated that short ET pathways through covalent bonds do not always result in ultrafast ET. We hypothesize that a rigid attachment of photosensitizers and efficient heat dissipation into the protein framework are needed for ultrafast ET. To test this hypothesis, we developed 13 new mutant forms of PpcA with the attachment cysteine sites showing restricted solvent exposure. We successfully labeled 11 out of 13 with Ru(bpy)3 and observed the expected complex masses in LC-MS. Analytical size-exclusion chromatography revealed the absence of aggregation and predominantly monomeric forms. Temperature-dependent circular dichroism (CD) spectroscopy showed the absence of any significant destabilization of the protein structure due to mutations and photosensitizer attachment, aside from I38CRu. Finally, we measured electron transfer rates that show that 10 of the 11 labeled PpcA-Ru(bpy)3 complexes show ultra-fast electron transfer.

Coupling of terahertz light with nanometre-wavelength magnon modes via spin–orbit torque

Spin-based technologies can operate at terahertz frequencies but require manipulation techniques that work at ultrafast timescales to become practical. For instance, devices based on spin waves, also known as magnons, require efficient generation of high-energy exchange spin waves at nanometre wavelengths. To achieve this, a substantial coupling is needed between the magnon modes and an electro-magnetic stimulus such as a coherent terahertz field pulse. However, it has been difficult to excite non-uniform spin waves efficiently using terahertz light because of the large momentum mismatch between the submillimetre-wave radiation and the nanometre-sized spin waves. Here we improve the light–matter interaction by engineering thin films to exploit relativistic spin–orbit torques that are confined to the interfaces of heavy metal/ferromagnet heterostructures. We are able to excite spin-wave modes with frequencies of up to 0.6 THz and wavelengths as short as 6 nm using broadband terahertz radiation. Numerical simulations demonstrate that the coupling of terahertz light to exchange-dominated magnons originates solely from interfacial spin–orbit torques. Our results are of general applicability to other magnetic multilayered structures, and offer the prospect of nanoscale control of high-frequency signals.

Tunable photon-induced spatial modulation of free electrons

Spatial modulation of electron beams is an essential tool for various applications such as nanolithography and imaging, yet its conventional implementations are severely limited and inherently non-tunable. Conversely, proposals of light-driven electron spatial modulation promise tunable electron wavefront shaping, for example, using the mechanism of photon-induced near-field electron microscopy. Here we present tunable photon-induced spatial modulation of electrons through their interaction with externally controlled surface plasmon polaritons (SPPs). Using recently developed methods of shaping SPP patterns, we demonstrate a dynamic control of the electron beam with a variety of electron distributions and verify their coherence through electron diffraction. Finally, the nonlinearity stemming from energy post-selection provides us with another avenue for controlling the electron shape, generating electron features far below the SPP wavelength. Our work paves the way to on-demand electron wavefront shaping at ultrafast timescales, with prospects for aberration correction, nanofabrication and material characterization.

Optical Creation of Skyrmions by Spin Reorientation Transition in Ferrimagnetic CoHo Alloys.

Manipulating magnetic skyrmions by means of a femtosecond (fs) laser pulse has attracted great interest due to their promising applications in efficient information-storage devices with ultralow energy consumption. However, the mechanism underlying the creation of skyrmions induced by an fs laser is still lacking. As a result, a key challenge is to reveal the pathway for the massive reorientation of magnetization from trivial to nontrivial topological states. Here, we studied a series of ferrimagnetic CoHo alloys and investigated the effect of a single laser pulse on the magnetic states. Thanks to the time-resolved magneto-optical Kerr effect and imaging techniques, we demonstrate that the laser-induced phase transitions from single domains into a topological skyrmion phase are mediated by the transient in-plane magnetization state, in real time and space domains, respectively. Combining experiments and micromagnetic simulations, we propose a two-step process for creating skyrmions through laser pulse irradiation: (i) the electron temperature enhancement induces a spin reorientation transition on a picosecond (ps) timescale due to the suppression of perpendicular magnetic anisotropy (PMA) and (ii) the PMA slowly restores, accompanied by out-of-plane magnetization recovery, leading to the generation of skyrmions with the help of spin fluctuations. This work provides a route to control skyrmion patterns using an fs laser, thereby establishing the foundation for further exploration of topological magnetism at ultrafast timescales.

Ultrafast protein response in the Pfr state of Cph1 phytochrome

Photoisomerization is a fundamental process in several classes of photoreceptors. Phytochromes sense red and far-red light in their Pr and Pfr states, respectively. Upon light absorption, these states react via individual photoreactions to the other state. Cph1 phytochrome shows a photoisomerization of its phycocyanobilin (PCB) chromophore in the Pfr state with a time constant of 0.7 ps. The dynamics of the PCB chromophore has been described, but whether or not the apoprotein exhibits an ultrafast response too, is not known. Here, we compare the photoreaction of 13C/15N labeled apoprotein with unlabeled apoprotein to unravel ultrafast apoprotein dynamics in Cph1. In the spectral range from 1750 to 1620 cm−1 we assigned several signals due to ultrafast apoprotein dynamics. A bleaching signal at 1724 cm−1 is tentatively assigned to deprotonation of a carboxylic acid, probably Asp207, and signals around 1670 cm−1 are assigned to amide I vibrations of the capping helix close to the chromophore. These signals remain after photoisomerization. The apoprotein dynamics appear upon photoexcitation or concomitant with chromophore isomerization. Thus, apoprotein dynamics occur prior to and after photoisomerization on an ultrafast time-scale. We discuss the origin of the ultrafast apoprotein response with the ‘Coulomb hammer’ mechanism, i.e. an impulsive change of electric field and Coulombic force around the chromophore upon excitation.Graphical abstract

Understanding the photodynamics of 3-hydroxypyran-4-one using surface hopping simulations

Photoinduced relaxation mechanisms of 3-hydroxypyran-4-one (3HOX) are explored by performing surface hopping dynamics simulations. Multiple conical intersections promote an internal conversion from higher singlet states to S1 within 50 fs. On a similar timescale, the intramolecular proton transfer occurs via a barrierless channel on S2. The proton-transferred (keto) tautomer then decays to its ground electronic state through an energetically accessible S1/S0 conical intersection. Eventually, the keto tautomer returns to S0 of enol form by back proton transfer. As events of the proton transfer cycle happen in the ultrafast timescale, 3HOX is expected to be highly photostable.

Pulsed far-infrared radiation of ferromagnetic heterojunction and its photothermal regulation

Under illumination of a femtosecond laser pulse on the Pt/CoFe/Ta trilayer heterostructure, an impulsive spin current can be generated in the ferromagnetic layer due to the ultrafast demagnetization. The spin current is super-diffusively transported and injected into the neighboring heavy metal layers, and is converted into the transversal charge current due to the spin-orbit coupling, which is named inverse spin Hall effect. The transient charge current on a time scale of sub-picosecond gives rise to the electromagnetic radiation in the far-infrared range to the free space. In this work, we demonstrate two kinds of experiments to investigate the modulation of far-infrared emission by photo-thermal effect, which is due to the thermal energy deposed by light pulses on a short timescales. First, the amplitude of the emitted far-infrared pulse as a function of an applied magnetic field is measured, which shows a far-infrared hysteresis behavior. The coercive field of the sample obtained by far-infrared hysteresis is smaller than that obtained by the <i>M</i>-<i>H</i> hysteresis through vibrating sample magnetometer. In addition, the coercive field decreases with pump laser fluence increasing. Second, the control of spin polarization on an ultrafast timescale in the presence of a small magnetic field applied oppositely to that of the magnetization of the ferromagnetic sample. The amplitude of far-infrared time-domain signal reaches a maximum value at a pump fluence of 1.43 mJ/cm<sup>2</sup>. For the pump fluence larger than 1.43 mJ/cm<sup>2</sup>, the far-infrared pulse experiences a phase reversal. After the reversal, a decrease of the laser pump fluence cannot restore the original phase of the far-infrared pulse. The above two experimental results not only elucidate the photothermal effect of femtosecond laser pulses, but also provide a new method for controlling the far-infrared radiation pulses based on ultrafast spintronics. These results demonstrate that far-infrared emission spectroscopy can be used as an ultrafast optical method to investigate magnetic properties, such as the coercive field and anisotropy field of the samples.

Shining a Spotlight on Photochemistry

Shining a Spotlight on Photochemistry

Floquet engineering in quantum materials

Floquet engineering based on the strong light-matter interaction is expected to drive quantum materials into nonequilibrium states on an ultrafast timescale, thereby engineering their electronic structure and physical properties, and achieving novel physical effects which have no counterpart in equilibrium states. In recent years, Floquet engineering has attracted a lot of research interest, and there have been numerous rich theoretical predictions. In addition, important experimental research progress has also been made in several representative materials such as topological insulators, graphene, and black phosphorus. Herein, we briefly introduce the important theoretical and experimental progress in this field, and prospect the research future, experimental challenges, and development directions.

Phonon-driven transient bandgap renormalization in perovskite single crystals.

Tailoring the electronic structure of perovskite materials on ultrafast timescales is expected to shed light on optimizing optoelectronic applications. However, the transient bandgap renormalization observed upon photoexcitation is commonly explained by many-body interactions of optically created electrons and holes, which shrink the original bandgap by a few tens of millielectronvolts with a sub-picosecond time constant, while the accompanying phonon-induced effect remains hitherto unexplored. Here we unravel a significant contribution of hot phonons in the photo-induced transient bandgap renormalization in MAPbBr3 single crystals, as evidenced by asymmetric spectral evolutions and transient reflection spectral shifts in the picosecond timescale. Moreover, we performed a spatiotemporal study upon optical excitation with time-resolved scanning electron microscopy and identified that the surface charge carrier diffusion and transient bandgap renormalization are strongly correlated in time. These findings highlight the need to re-evaluate current theories on photo-induced bandgap renormalization and provide a new approach for precisely controlling the optical and electronic properties of perovskite materials, enabling the design and fabrication of high-performance optoelectronic devices with exceptional efficiency and unique properties.

Atom-Specific Probing of Electron Dynamics in an Atomic Adsorbate by Time-Resolved X-Ray Spectroscopy.

The electronic excitation occurring on adsorbates at ultrafast timescales from optical lasers that initiate surface chemical reactions is still an open question. Here, we report the ultrafast temporal evolution of x-ray absorption spectroscopy (XAS) and x-ray emission spectroscopy (XES) of a simple well-known adsorbate prototype system, namely carbon (C) atoms adsorbed on a nickel [Ni(100)] surface, following intense laser optical pumping at 400nm. We observe ultrafast (∼100 fs) changes in both XAS and XES showing clear signatures of the formation of a hot electron-hole pair distribution on the adsorbate. This is followed by slower changes on a few picoseconds timescale, shown to be consistent with thermalization of the complete C/Ni system. Density functional theory spectrum simulations support this interpretation.

Diabatic and adiabatic transitions between Floquet states imprinted in coherent exciton emission in monolayer WSe 2

Floquet engineering is a promising way of controlling quantum system with photon-dressed states on an ultrafast time scale. So far, the energy structure of Floquet states in solids has been intensively investigated. However, the dynamical aspects of the photon-dressed states under ultrashort pulse have not been explored yet. Their dynamics become highly sensitive to the driving field transients, and thus, understanding them is crucial for ultrafast manipulation of a quantum state. Here, we observed the coherent exciton emission in monolayer WSe2 at room temperature at the appropriate photon energy and the field strength of the driving light pulse using high-harmonic spectroscopy. Together with numerical calculations, our measurements revealed that the coherent exciton emission spectrum reflects the diabatic and adiabatic dynamics of Floquet states of excitons. Our results provide a previosuly unexplored approach to Floquet engineering and lead to control of quantum materials through pulse shaping of the driving field.

Nature of the Ultrafast Interligands Electron Transfers in Dye-Sensitized Solar Cells.

Charge-transfer dynamics and interligand electron transfer (ILET) phenomena play a pivotal role in dye-sensitizers, mostly represented by the Ru-based polypyridyl complexes, for TiO2 and ZnO-based solar cells. Starting from metal-to-ligand charge-transfer (MLCT) excited states, charge dynamics and ILET can influence the overall device efficiency. In this letter, we focus on N34- dye ( [Ru(dcbpy)2(NCS)2]4-, dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) to provide a first direct observation with high time resolution (<20 fs) of the ultrafast electron exchange between bpy-like ligands. ILET is observed in water solution after photoexcitation in the ∼400 nm MLCT band, and assessment of its ultrafast time-scale is here given through a real-time electronic dynamics simulation on the basis of state-of-the-art electronic structure methods. Indirect effects of water at finite temperature are also disentangled by investigating the system in a symmetric gas-phase structure. As main result, remarkably, the ILET mechanism appears to be based upon a purely electronic evolution among the dense, experimentally accessible, MLCT excited states manifold at ∼400 nm, which rules out nuclear-electronic couplings and proves further the importance of the dense electronic manifold in improving the efficiency of dye sensitizers in solar cell devices.

Femtosecond Extreme Ultraviolet Spectroscopy of an Iridium Photocatalyst Reveals Oxidation State and Ligand Field Specific Dynamics

Femtosecond X-ray absorption spectroscopy at the Ir O3-edge and N6,7-edges is performed on the photocatalyst iridium(III) tris(2-phenylpyridine), Ir(III)(ppy)3 using a tabletop high-harmonic source. Extreme ultraviolet (XUV) absorption between 44 and 76 eV measures transitions from the Ir 5p3/2 and 4f5/2,7/2 core to 5d valence orbitals, and the position of these spectral features is shown to be sensitive to the oxidation state and ligand field of the metal center. Upon excitation of the singlet metal-to-ligand charge transfer (1MLCT) band at 400 nm, a shift in the spectra due to the formation of the Ir(IV) center is observed, as is the creation of a new spectral feature corresponding to transitions into the t2g hole. Vibrational cooling of the MLCT state on the 3 and 16 ps time scales is measured as changes in the intensity of the transient features. This work establishes XUV spectroscopy as a useful tool for measuring the electronic structure of third row transition metal photosensitizers and catalysts at ultrafast time scales.

Completely Anisotropic Ultrafast Optical Switching and Direction‐Dependent Photocarrier Diffusion in Layered ZrTe5

AbstractLayered nanomaterials with in‐plane anisotropy exhibit unique orientation‐dependent responses to external stimuli, enabling the development of novel devices with additional degrees of freedom. In particular, their anisotropic optical properties enable ultrafast nanophotonic modulators to be controlled by light polarization. However, achieving high controllability is still challenging due to incomplete optical anisotropy in most materials. Here, this work presents a completely anisotropic, ultrafast optical modulation in zirconium pentatelluride (ZrTe5), a layered nanomaterial that has recently attracted renewed attention. The transient absorption (TA) microscopy reveals anisotropic ultrafast picosecond optical modulation in a broad range of 1.2–2.2 eV. In particular, at a certain photon‐energy of 1.62 eV, complete on/off switching with a near‐unity degree of anisotropy is achieved solely by changing the light polarization, suggesting that ZrTe5 is a promising material for polarization‐selective high‐speed optical modulators. The theoretical analysis of the transition dipole moments attributes this sharp anisotropy to strongly polarization‐dependent excited‐state absorption. Furthermore, this work directly observes direction‐dependent photocarrier transport using scanning TA microscopy. It yields the anisotropic diffusivity, mobility, and diffusion lengths of the photocarriers, which are essential parameters for designing devices. Therefore, this work provides a comprehensive understanding of the anisotropic optical characteristics of ZrTe5 on ultrafast timescales.

Distant Symmetry Control in Electron-Induced Bond Cleavage.

We experimentally show that N-H bond cleavage in the pyrrole molecule following resonant electron attachment is allowed and controlled by the motion of the atoms which are not dissociating, namely, of the carbon-attached hydrogen atoms. We use this fact to steer the efficiency of this bond cleavage. In order to interpret the experimental findings, we have developed a method for locating all resonant and virtual states of an electron-molecule system in the complex plane, based on all-electron R-matrix scattering calculations. Mapping these as a function of molecular geometry allows us to separate two contributing dissociation mechanisms: a π* resonance formation inducing strong bending deformations and a nonresonant σ* mechanism originating in a virtual state. The coupling between the two mechanisms is enabled by the out-of-plane motion of the C-H bonds, and we show that it must happen on an ultrafast (few fs) time scale.