Achieving parametric excitation in an oscillating physical system involves periodically adjusting one of its parameters to modulate the oscillator's natural frequency. This phenomenon has been observed in numerous systems within physics and engineering, profoundly transforming modern science and technology. Despite rapid progress, the parametric control of collective excitations, such as phonons, remains a challenge while promising to generate novel and intriguing effects in a largely unexplored field. Here, we investigate the terahertz (THz) field-induced dynamics of Raman-active phonons in the perovskite structure of LaAlO_{3}. Utilizing intense THz pulses, we demonstrate a novel mechanism of parametric phonon excitation marked by substantial subharmonic components. Theoretical analysis can successfully capture the hallmarks of the observed phenomena in a physical scenario with the THz field inducing a parametric coupling between the Raman mode and pairs of acoustic phonon excitations.

The disulfide bond, in the form of cystine, plays a key role in protein structure and function. Dimethyl disulfide serves as a model system for understanding the fundamental properties of this unique chemical bond, including its response to UV photoexcitation. While photoexcitation at 267 nm is known to exclusively cleave the S–S bond on a sub-picosecond time scale, photoexcitation at 200 nm excites a mixture of electronic states of Rydberg and antibonding character along the C–S bond, resulting in competing dissociation pathways on an unknown timescale. Herein, we use mega-electron-Volt ultrafast electron diffraction and time-resolved velocity-mapped ion imaging to directly time the competing C–S and S–S bond dissociation pathways upon photoexcitation of dimethyl disulfide at 200 nm, finding sub-picosecond as well as unexpectedly long, picosecond lifetimes. Non-adiabatic mixed quantum-classical trajectories reveal pathways for each bond dissociation and help interpret experimental results through calculations of both experimental observables. We suggest that while the sub-picosecond dynamics arise from bond dissociation on the singlet manifold, picosecond dynamics arise from

Photo-induced ferroelectricity in the quantum paraelectric SrTiO_3 involves the dynamical interplay between a coherently driven Ti-O stretching vibration and multiple structural degrees of freedom, including antiferrodistortive rotations, strain, and the polar mode instability. In the high-temperature cubic phase, in the absence of average antiferrodistortion, time-resolved X-ray diffuse scattering has evidenced a correlation between a photo-induced reduction in antiferrodistortive fluctuations and the emergence of ferroelectric order. Here, we complement these measurements with time-resolved elastic X-ray diffraction in the low-temperature tetragonal phase, in which antiferrodistortive fluctuations are small but a finite average rotation has set in. In this phase, we observe a long-lived reduction of the equilibrium antiferrodistortive rotation angle. A unified theory of the nonlinear lattice dynamics based on first-principles calculations describes the dynamics in both high-temperature cubic and low-temperature tetragonal phases, providing a basis for light-induced ferroelectricity in SrTiO_3.

Disulfide photochemistry impacts a wide range of chemical processes from biological UV photodamage to polymer self-healing and green photocatalysis. Despite this, the response of disulfide bonds to deep‑UV light remains poorly understood. Dimethyl disulfide serves as a model system for understanding the fundamental properties of this chemical motif, including its UV photodynamics. While 267-nm excitation exclusively cleaves the S–S bond on a sub-picosecond timescale, 200 nm excites electronic states of Rydberg and antibonding character, resulting in competing C–S and S–S dissociation on an unknown timescale. Using mega-electron-Volt ultrafast electron diffraction and time-resolved velocity-mapped ion imaging, we find sub-picosecond as well as unexpectedly long, picosecond lifetimes. Non-adiabatic mixed quantum-classical dynamics reveal mechanisms and observables. We attribute the sub-picosecond dynamics to bond dissociation on singlet states and the picosecond dynamics to dissociation after intersystem crossing. Our study reveals that deep-UV excitation in disulfide-containing molecules can induce complex, multi-timescale dynamics.

Ultrafast polarization dynamics in ferroelectrics are of considerable interest for high-speed tunable dielectrics and electro-optics. Extended domain wall networks formed in ferroelectric twin nanodomains can support collective dynamics in the terahertz regime but require techniques that track polarization and strain evolution driven by ultrafast stimulus. Here, we use multi-modal probing of THz-pulse-driven excitations in PbTiO3/SrTiO3 superlattices by combining X-ray free electron laser measurements that directly tracks lattice changes, with optical second harmonic generation that tracks the electronic potential coupled with the lattice potential. Dynamical phase-field modeling enables fingerprinting of these collective modes as superpositions of domain "breathing" through wall oscillations and polarization "rotations" with still walls. Ultrafast domain wall motion at 0.1-0.5 THz is observed at practical fields of 100 kV/cm with wall velocities of >4000 m/s, approaching typical speed of sound in PbTiO3. A unique "charging" mode is discovered that can electrically charge and discharge domain walls on ∼4 ps time scale thus dynamically tuning wall conductivity. Integrated experimental and theoretical fingerprinting of the dynamical landscape presented here enables ultrafast control of ferroics for high-speed microelectronics and optical applications.

Strong-field terahertz (THz) excitations enable dynamic control over electronic, lattice and symmetry degrees of freedom in quantum materials. Here, we uncover pronounced terahertz-induced symmetry modulations and coherent phonon dynamics in the van der Waals antiferromagnet MnPS3, in which inversion symmetry is broken by its antiferromagnetic spin configuration. Time-resolved second harmonic generation measurements reveal long-lived giant oscillations in the antiferromagnetic phase, with amplitudes comparable to the equilibrium signal, driven by phonons involving percent-level atomic displacements relative to the equilibrium bond lengths. The temporal evolution of the rotational anisotropy patterns indicate a dynamic breaking of mirror symmetry, modulated by two vibrational modes at 1.7 THz and 4.5 THz, with the former corresponding to a hidden mode not observed in equilibrium spectroscopy. We show that these effects arise in part from a field-induced charge rearrangement mechanism that lowers the local crystal symmetry, and couples to the phonon modes. A long-lived field-driven response was uncovered with a complex THz polarization dependence which, in comparison to theory, indicates evidence for an antiferromagnetic-to-ferrimagnetic transition. Our results establish an effective field-tunable pathway for driving excitations otherwise weak in equilibrium, and for manipulating magnetism in low-dimensional materials via dynamical modulation of symmetry.

Laser ablation is a process that bears both fundamental physics interest and has wide industrial applications. For decades, the lack of probes on the relevant time and length scales has prevented access to the highly nonequilibrium phase decomposition processes triggered by laser excitation. In this study, a close integration of time-resolved probing by intense femtosecond X-ray pulses with large-scale atomistic modeling has yielded unique insights into the ablation dynamics of thin gold films irradiated by femtosecond laser pulses. The emergence and growth of nanoscale density heterogeneities in the expanding ablation plume, predicted in the simulations, are mapped to the rapid evolution of distinct small angle diffraction features. This mapping enables identification of the characteristic signatures of different phase decomposition processes occurring simultaneously in the plume, which are driven by photomechanical and thermodynamic driving forces. Beyond the specific insights into the ablation phenomenon, this study demonstrates the power of joint X-ray probing and atomistic modeling of material dynamics under extreme conditions of thermal and mechanical nonequilibrium.

We realize single-crystal freestanding NiO films on SiN membranes, enabling thin-film scattering experiments with little or no substrate background signal. These membrane samples provide a critical platform for performing ultrafast electron diffraction (UED) to probe the response of the lattice to laser excitation. We show that epitaxial NiO films on a water-soluble Sr2CaAl2O6 buffer layer on SrTiO3 substrates can be transferred as freestanding films to the SiN membranes while maintaining the epitaxial character of the films. An above-gap photoexcitation (lambda = 266 nm) incident on the sample stimulates an initial lattice response of the order of 1.1 ps, followed by the persistence of this state for more than 20 ps. We observe typical Debye-Waller behavior in peaks with q above the (220) family, but a distinct deviation from this behavior is seen in low-q peaks. We relate this behavior to a dynamic decrease in sample mosaicity in response to the optical pump of the order of 3% that endures for approximately 4 ps. We suspect that this dynamic mosaicity is due to laser-induced strain propagation. This work demonstrates the viability of the thin-film transfer method for UED and paves the way for the study of the dynamic response of antiferromagnetic thin-film oxides.

The nature of the "failed" ferroelectric transition in SrTiO3 has been a long-standing puzzle in condensed matter physics. A compelling explanation is the competition between ferroelectricity and an instability with a mesoscopic modulation of the polarization. These polarization density waves, which should become especially strong near the quantum critical point, break local inversion symmetry and are difficult to probe with conventional x-ray scattering methods. Here we combine a femtosecond x-ray free electron laser (XFEL) with THz coherent control methods to probe inversion symmetry breaking at finite momenta and visualize the instability of the polarization on nanometer lengthscales in SrTiO3. We find polar-acoustic collective modes that are soft particularly at the tens of nanometer lengthscale. These precursor collective excitations provide evidence for the conjectured mesoscopic modulated phase in SrTiO3.

Attosecond photoemission or photoionization delays are a unique probe of the structure and the electronic dynamics of matter. However, the spectral congestion of valence photoelectron spectra sets fundamental limits to the complexity of systems that can be studied, and the delocalization of valence electron wave functions blurs the spatial origin of the photoelectron wave packet. Using attosecond x-ray pulses from LCLS, we demonstrate the key advantages of measuring core-level delays: The photoelectron spectra remain atomlike, the measurements become element specific, and the observed scattering dynamics originate from a pointlike source when multicenter interference effects are negligible. We exploit these unique features to reveal the effects of changing functional groups (C-H vs N) and symmetry on attosecond scattering dynamics by measuring and calculating the photoionization delays between N-1s and C-1s core shells of a series of aromatic azabenzene molecules. Remarkably, the delays increase with the number of nitrogen atoms in the molecule and reveal multiple resonances. We identify two previously unknown mechanisms regulating the associated attosecond dynamics, namely the enhanced confinement of the trapped wave function with the replacement of C-H groups by N atoms and the decrease of the coupling strength among the photoemitted partial waves with increasing symmetry. This study demonstrates the unique opportunities opened by measurements of core-level photoionization delays for unraveling attosecond electron dynamics in complex matter.

Driving coherent lattice motion with THz pulses has emerged as a novel pathway for achieving dynamic stabilization of exotic phases that are inaccessible in equilibrium quantum materials. In this Letter, we present a previously unexplored mechanism for THz excitation of Raman-active phonons. We show that intense THz pulses centered at 1 THz can excite the Raman-active A_{1g} phonon mode at 2.9 THz in a bismuth film. We rule out the possibilities of the phonon being excited through conventional anharmonic coupling to other modes or via a THz sum frequency process. Instead, we demonstrate that the THz-driven tunnel ionization provides a plausible means of creating a displacive driving force to initiate the phonon oscillations. Our Letter highlights a new mechanism for exciting coherent phonons, offering potential for dynamic control over the electronic and structural properties of semimetals and narrow-band semiconductors on ultrafast timescales.

The past decades have witnessed the development of new X-ray beam sources with brightness growing at a rate surpassing Moore's law. Current and upcoming diffraction limited and fully coherent X-ray beam sources, including multi-bend achromat based synchrotron sources and high repetition rate X-ray free electron lasers, puts increasingly stringent requirements on stability and accuracy of X-ray optics systems. Parasitic motion errors at sub-micro radian scale in beam transport and beam conditioning optics can lead to significant loss of coherence and brightness delivered from source to experiment. To address this challenge, we incorporated optical metrology based on interferometric length and angle sensing and real-time correction as part of the X-ray optics motion control system. A prototype X-ray optics system was constructed following the optical layout of a tunable X-ray cavity. On-line interferometric metrology enabled dynamical feedback to a motion control system to track and compensate for motion errors. The system achieved sub-microradian scale performance, as multiple optical elements are synchronously and continuously adjusted. This first proof of principle measurement demonstrated both the potential and necessity of incorporating optical metrology as part of the motion control architecture for large scale X-ray optical systems such as monochromators, delay lines, and in particular, X-ray cavity systems to enable the next generation cavity-based X-ray free electron lasers.

Interfacial thermal and acoustic phenomena have an important role in quantum science and technology, including in spintronic and spincaloritronic materials and devices. Simultaneous measurements of the low-temperature thermal and acoustic properties of a metal/insulator heterostructure reveal distinct dynamics in the characteristic phonon frequency ranges of acoustic and thermal transport. The measurements probed a heterostructure consisting of a thin film of Pt on the ferrimagnetic insulator gadolinium iron garnet (Gd3Fe5O12, GdIG) grown epitaxially on a gadolinium gallium garnet substrate. Ultrafast structural dynamics within the Pt layer were tracked using time-resolved ultrafast x-ray diffraction and analyzed to probe interfacial acoustic and thermal properties. The rapid heating of the Pt layer by a 400 nm wavelength femtosecond-duration optical pulse produced transient structural changes that provided the stimulus for these measurements. Rapid heating produced a broadband acoustic pulse that was partially reflected by the Pt/GdIG interface. Temporal frequencies up to 740 GHz, corresponding to angular frequencies of several THz, were detected in a wavelet analysis of the acoustic oscillations of the strain in the Pt layer. The structural results were analyzed to determine (i) the acoustic damping coefficient and phonon mean free path in Pt at frequencies of hundreds of GHz and (ii) the Grüneisen anharmonicity parameter. The thermal conductance of the Pt/GdIG interface was tracked using the slower, tens-of-picosecond-scale, dynamics of the initial cooling of the heated Pt layer. Analysis using a model based on the Boltzmann transport equation shows that the phonon transmission is lower at the phonon frequencies relevant to thermal transport than for subterahertz regime acoustics.

Terahertz (THz) generation by optical rectification in LiNbO_3 (LN) is a widely used technique for generating intense THz radiation. The spatiotemporal characterization of THz pulses from these sources is currently limited to far-field methods. While simulations of tilted pulse front THz generation have been published, little work has been done to measure the near-field properties of the THz source. A better understanding of the THz near-field properties will improve optimization of THz generation efficiency, transport, and coupling. We demonstrate a technique for quantitative spatiotemporal characterization of single-cycle strong-field THz pulses with 2D near-field electro-optic imaging. We have reconstructed the full temporal 3D THz near-field and shown how the phase front can be tailored by controlling the incident pump pulse.

Unraveling collective modes arising from coupled degrees of freedom is crucial for understanding complex interactions in solids and developing new functionalities. Unique collective behaviors emerge when two degrees of freedom, ordered on distinct length scales, interact. Polar skyrmions, three-dimensional electric polarization textures in ferroelectric superlattices, disrupt the lattice continuity at the nanometer scale with nontrivial topology, leading to previously unexplored collective modes. Here, using terahertz-field excitation and femtosecond x-ray diffraction, we discover subterahertz collective modes, dubbed "skyrons", which appear as swirling patterns of atomic displacements functioning as atomic-scale gearsets. The key to activating skyrons is the use of the THz field that couples primarily to skyrmion domain walls. Momentum-resolved time-domain measurements of diffuse scattering reveal an avoided crossing in the dispersion relation of skyrons. Atomistic simulations and dynamical phase-field modeling provide microscopic insights into the three-dimensional crystallographic and polarization dynamics. The amplitude and dispersion of skyrons are demonstrated to be controlled by sample temperature and electric-field bias. The discovery of skyrons and their coupling with terahertz fields opens avenues for ultrafast control of topological polar structures.

Highly covalent Ni bis(dithiolene) and related complexes provide an ideal platform for investigating the effects of metal-ligand orbital hybridization on excited state character and dynamics. In particular, we focus on the ligand field excited states that dominate the photophysics of first-row transition metal complexes. We investigate if they can be significantly delocalized off the metal center, possibly yielding photochemical reactivity more similar to charge transfer excited states than metal-centered ligand field excited states. Here, [Ni(mpo)2] (mpo = 2-mercaptopyridine-N-oxide) provides a representative example for the larger chemical class and is an active electro- and photocatalyst for proton reduction. A detailed characterization of the excited state electronic structure, dynamics, and photochemistry of [Ni(mpo)2] is presented based on ultrafast transient X-ray absorption spectroscopy at the Ni and S 1s core absorption K-edges. By comparing the ultrafast Ni K-edge absorption to ab initio calculations, we identify an excited state relaxation mechanism where an initial ligand-to-metal charge transfer excitation results in both excited state electron transfer (generating a catalytically relevant reduced photoproduct [Ni(mpo)2]-) and relaxation to a pseudotetrahedral triplet ligand field excited state. From the ultrafast S K-edge absorption, the ligand field excited state is found to be highly delocalized onto the thiolate ligands, and a tetrahedral structural distortion is shown to substantially influence the degree of delocalization. The results identify a significant structural coordinate to target when aiming to control the excited state covalency in square planar complexes.

We demonstrate a multidimensional pump-probe technique that dynamically modulates and detects rotational symmetries in second harmonic generation (SHG) from MnPS3, revealing intrinsic six-fold symmetry, THz-induced two-fold symmetry, and a tran-sient, four-fold component indicating symmetry breaking processes. © 2024 The Author(s)

Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps towards understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species amongst the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initio molecular dynamics calculations offer a powerful route to determining time-resolved populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5H)-thiophenone. This strategy provides experimental validation of the predicted high (~50%) yield of an episulfide isomer containing a strained 3-membered ring within ~1 ps of photoexcitation and highlights the rapidity of interconversion between the rival highly vibrationally excited photoproducts in their ground electronic state.

Ultrafast stimuli can stabilize metastable states of matter inaccessible by equilibrium means. Establishing the spatiotemporal link between ultrafast excitation and metastability is crucial to understanding these phenomena. Here, we use single-shot optical-pump, X-ray-probe measurements to provide snapshots of the emergence of a persistent polar vortex supercrystal in a heterostructure that hosts a fine balance between built-in electrostatic and elastic frustrations by design. By perturbing this balance with photoinduced charges, a starting heterogenous mixture of polar phases disorders within a few picoseconds, resulting in a soup state composed of disordered ferroelectric and suppressed vortex orders. On the pico-to-nanosecond timescales, transient labyrinthine fluctuations form in this soup along with a recovering vortex order. On longer timescales, these fluctuations are progressively quenched by dynamical strain modulations, which drive the collective emergence of a single supercrystal phase. Our results, corroborated by dynamical phase-field modeling, reveal how ultrafast excitation of designer systems generates pathways for persistent metastability.