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At least 19 records

Extracting spinon self-energies from two-dimensional coherent spectroscopy

Two-dimensional coherent spectroscopy (2DCS) is a nonlinear spectroscopy technique capable of identifying whether apparent continua in linear response are made out of multiplets of sharp deconfined quasiparticles. This makes it a potent tool for experimental identification of fractionalized phases. Previous discussions have focused on limits where the quasiparticles in question are infinitely long lived. In this paper we discuss 2DCS in the regime where the fractionalized quasiparticles can themselves decay. We introduce a powerful path-integral-based approach, whereby the computation of nonlinear susceptibilities reduces to an efficient exercise in diagrammatic perturbation theory. Here, we apply this method to compute the 2DCS response of the one-dimensional transverse field Ising model, in the presence of integrability-breaking perturbations. We discuss aspects of the self-energy of the fractionalized quasiparticles that may be extracted via 2DCS, such as the momentum-dependent decay rate.

1-dimensional spin chains↗

Terahertz 2D coherent spectroscopy for probing and controlling multicorrelations in quantum matter

Terahertz 2D coherent spectroscopy (THz-2DCS) is an emerging technique that brings multidimensional resolution to the ultrafast spectral–temporal dynamics of non-equilibrium quantum phases of matter, enabling new capabilities for precise coherent control in many-body dynamics and multiorder correlations. Here, by mapping and disentangling complex excitation and detection pathways across distinct time and frequency dimensions, THz-2DCS provides a form of coherence tomography of light-induced quantum matter — revealing multiquantum coherences, separating nonlinear response functions and capturing collective modes and quantum kinetics on ultrafast THz timescales. This Perspective discusses the technical capabilities of THz-2DCS, provides a comparison to other multidimensional and coherent transient spectroscopies and looks ahead towards opportunities for advancing THz-2DCS instrumentation and experimental strategies towards new frontier discoveries.

Huang, Chuankun [Ames Laboratory (AMES), Ames, IA ↗

Probing molecular wavepacket evolution using multidimensional coherent spectroscopy (Final Report)

The goal of this project was to develop and demonstrate multidimensional coherent spectroscopy (MDCS) techniques to fully map wave-packet dynamics in simple molecules. MDCS correlates excitation and emis sion frequencies, enabling continuous tracking of wave-packet evolution even when multiple wave-packets evolve simultaneously. The initial experiments were to be performed using the MDCS apparatus in the PI’s laboratory to record the evolution of the wave-packet’s energy in molecular iodine. A longer-term goal was to develop a version compatible with using an X-ray Free Electron Laser (XFEL) as a probe, which would allow the evolution of the internuclear distance of the wave-packet—not just its energy—to be determined.

74 ATOMIC AND MOLECULAR PHYSICS↗

Multidimensional Coherent Spectroscopy of van der Waals materials and heterostructures (Final Technical Report)

This project advanced multidimensional coherent spectroscopy (MDCS) and related spectroscopic-imaging methods as quantitative probes of many-body optical excitations in two-dimensional (2D) van der Waals (vdW) semiconductors and their heterostructures. Monolayer transition-metal dichalcogenides (TMDs) such as MoSe 2 and WSe 2 provide a uniquely strong platform for excitonic physics due to reduced dielectric screening, which enhances Coulomb interactions and makes higher-order correlated states (e.g., biexcitons and exciton–trion correlations) more prominent than in conventional bulk semiconductors. At the same time, the same sensitivity that enables strong interactions also increases susceptibility to spatial inhomogeneity—e.g., strain gradients, wrinkles, nanoscale disorder potentials, and charge puddling—which can broaden resonances, obscure interaction signatures, and complicate device-to-device reproducibility. The work reported here addressed this dual opportunity and challenge by: (i) developing and deploying coherent multidimensional methods (including double-quantum MDCS) capable of isolating interaction signals with reduced background, (ii) integrating electrostatic control to tune carrier populations and interaction strengths in situ, and (iii) introducing complementary spatially resolved photoluminescence (PL) techniques—hyperspectral PL imaging and polarization-/field-dependent PL lineshape analysis—to directly quantify disorder, strain, and localization that govern the coherent response.

36 MATERIALS SCIENCE↗

Multidimensional coherent spectroscopy of light-driven states and their collective modes in multiband superconductors

We present a comprehensive theory of light-controlled multiband superconductivity, and apply it to predict distinctive signatures of light-driven superconducting (SC) states in terahertz multidimensional coherent spectroscopy (THz-MDCS) experiments. We first derive gauge-invariant Maxwell-Bloch equations for multiband BCS superconductors with spatial fluctuations. We consider driving electromagnetic fields determined self-consistently by Maxwell's equations. By calculating the THz-MDCS spectra measured experimentally in the clean SC limit, we identify unique signatures of finite-momentum Cooper-pairing states that live longer than the laser pulse. They are controlled by a pair of THz laser pulses with well-defined relative phase (pulse pair). The pseudospin oscillators that describe the properties of these SC states are parametrically driven by both finite-momentum Cooper pairing and by time oscillations of the order-parameter relative phase. We show that such strong parametric driving leads to drastic changes in the THz-MDCS spectral shape from the predictions of third-order nonlinear susceptibility calculations. These spectral changes strongly depend on the interband-to-intraband interaction ratio and on the collective modes of the light-driven state. For negligible interband interaction, the spectra show a transition with increasing field, from traditional pump-probe, four-wave-mixing, and third-harmonic generation peaks determined by the laser frequency to sidebands determined by the excitations of the driven system. These sidebands emerge from difference-frequency Raman processes in the nonequilibrium SC state. For interband couplings weaker than the intraband pairing, we show that the Leggett phase collective mode leads to harmonic sidebands around the traditional pump-probe peaks. Additional Higgs collective mode peaks result from light-induced inversion-symmetry breaking in a thin-film geometry. For strong interband coupling, we find a transition from a nonequilibrium finite Cooper-pair momentum state characterized by hybrid-Higgs amplitude mode peaks in THz-MDCS spectra to a driven state identified experimentally by the emergence of Floquet-type sidebands at bi-Higgs frequencies. Those dominant bi-Higgs-frequency satellites are manifestations of a new order parameter relative phase collective mode that characterizes the nonequilibrium SC state. The predicted interaction- and field-dependent transitions in the spectral profile allow us to propose THz-MDCS experiments for quantum tomography of light-driven superconductivity.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Observation of cupratelike nonlinear terahertz responses in superconducting infinite-layer nickelates via two-dimensional coherent spectroscopy

The 𝑑-wave pairing symmetry in newly discovered infinite-layer nickelates remains highly debated compared to the widely accepted 𝑑-wave superconductivity in cuprates, despite recent intense efforts using equilibrium optical and electrical transport measurements. A complementary approach involves characterizing THz coherent nonlinear responses, which is currently lacking but needed, as it would offer new insights into the superconducting gap structure by characterizing Higgs modes and quasiparticle excitations. Here, in this study, we report THz 2D coherent spectroscopy (THz-2DCS) responses from the superconducting state in an infinite-layer nickelate. The 2D spectra clearly demonstrate the absence of hallmark signatures of 𝑠-wave pairing symmetry, such as resonant 2⁢Δ peaks at superconducting gaps. Instead, we observe gapless 2D spectra in the nickelate, centered around the THz driving frequency, with no noticeable shift as the temperature increases. These findings closely resemble the nodal superconductivity behavior expected in cuprates. Together with our simulations, these findings suggest that 2⁢Δ signatures in the 2D spectra of 𝑑-wave gap structures can be obscured by significant nodal quasiparticle excitations at arbitrarily low energies. This contrasts with the long-lived Higgs modes, observed as distinct 2⁢Δ peaks in a controlled THz-2DCS experiment on niobium, a representative example of dirty-limit s-wave superconductors. Our results have implications for understanding the unconventional superconductivity in nickelates and highlight the need to explore their coherent nonlinear dynamics.

Pairing mechanisms↗

Perspective: multi-dimensional coherent spectroscopy of perovskite nanocrystals

Abstract Recently, colloidal perovskite nanocrystals (PNCs) have emerged as an exciting material platform for optoelectronic applications due to their combination of facile synthesis routes, quantum size effects, and exceptional optical properties among other favorable characteristics. Given the focus on their optoelectronic properties, spectroscopic characterization of PNCs is crucial to rational design of their structure and device implementation. In this Perspective, we discuss how multi-dimensional coherent spectroscopy (MDCS) can resolve exciton dynamics and circumvent inhomogeneous broadening to reveal underlying homogeneous spectral lineshapes. We highlight recent applications of MDCS to PNCs in the literature, and suggest compelling problems concerning their microscopic physics to be addressed by MDCS in the future.

Liu, Albert (ORCID:0000000167183719)↗

Optical interference effect in strong-field electronic coherence spectroscopy

Here, we investigate strong-field-induced electronic coherences in argon and molecular nitrogen ions created by high-intensity, few-cycle infrared laser pulses. This is a step toward the long-sought goal of strong-field coherent control in molecular chemistry. We employ high-intensity, few-cycle infrared laser pulses in a pump-probe setup to investigate a recent prediction that electronic coherences in nitrogen molecules change the ion yields versus pump-probe delay. [Yuen et al., Phys. Rev. A 109, L011101 (2024)]. The predicted coherence signals in molecular nitrogen could not be resolved above the optical interference of the pump and probe pulses; a simultaneous measurement clearly resolved the induced cation fine-structure coherence in strong-field-ionized argon. The results of our comparison with simulations suggest that optical interference effects manifest differently in each ionic species and must be carefully accounted for when interpreting experimental data. We find that nonsequential double ionization in the low-intensity region of the focal volume can reduce the visibility of coherence generated by two-pulse sequential ionization, and we quantify the importance of pulse shape and spectral characteristics for isolating the desired coherence signals.

charge migration↗

Rotation in attosecond vibronic coherence spectroscopy for molecules

Abstract Excitation or ionization of a molecule by ultrafast laser pulses can create a superposition of electronic states, whose dynamics is influenced by the interplay of electronic coherence and nuclear motion, resulting in charge migration and possibly charge transfer. Probing the vibronic coherence is therefore vital to monitoring electronic dynamics and controlling chemical reactivity, as recently demonstrated in molecules via attosecond transient absorption spectroscopy (ATAS). However, theories supporting the interpretation of ATAS experiments neglect the effects of molecular rotation, often leading to inaccurate interpretation of experimental data. Here, we develop a comprehensive theory for ATAS of molecules encompassing the entire pump-probe process. Applying the theory to N 2 , we demonstrate that the emergence of coherent signals critically depends on the consideration of molecular rotation. This work contributes to close the gap between theory and ATAS experiments, paving the way for monitoring electronic motion and controlling chemical reactivity in diverse molecular systems.

Physics↗

Multidimensional Coherent Spectroscopy of Molecular Polaritons: Langevin Approach

We present a microscopic theory for nonlinear optical spectroscopy of N molecules in an optical cavity. Using the Heisenberg-Langevin equation, an analytical expression is derived for the time- and frequency-resolved signals accounting for arbitrary numbers of vibrational excitations. We identify clear signatures of the polariton-polaron interaction from multidimensional projections of the signal, e.g., pathways and timescales. Cooperative dynamics of cavity polaritons against intramolecular vibrations is revealed, along with a crosstalk between long-range coherence and vibronic coupling that may lead to localization effects. Our results further characterize the polaritonic coherence and the population transfer that is slower.

74 ATOMIC AND MOLECULAR PHYSICS↗

Visualization and quantum control of light-accelerated condensates by terahertz multi-dimensional coherent spectroscopy

Abstract Characterizing and controlling high-order correlation of quantum systems is key for developing quantum devices and switching technologies. Although conventional static and ultrafast spectroscopy gives access to collective excitations characterizing quantum states, more exotic correlations cannot be easily separated from other contributions. Here we develop density matrix simulations to show that seventh-order-wave-mixing peaks with distinct temperature and field dependences in two-dimensional terahertz nonlinear spectra reveal light-induced correlations in non-equilibrium superconducting states. Above critical terahertz driving, these emerging peaks split from conventional peaks along the second axis introduced by pump-probe relative phase in two-dimensional frequency space. They are photo-generated by correlations between two-photon fluctuations and interacting quasi-particle and quasi-particle/Higgs superconductor excitations. By photo-inducing persistent symmetry breaking via light-wave propagation, we also demonstrate seventh-order-wave-mixing sensing of Higgs collective modes. Our theory suggests to use multi-dimensional spectroscopy for quantum sensing of light-driven superconductivity and paves a path for quantum operations by few-cycle-THz-periodic photocurrent modulation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Characterizing coherences in chemical dynamics with attosecond time-resolved x-ray absorption spectroscopy

Coherence can drive wave-like motion of electrons and nuclei in photoexcited systems, which can yield fast and efficient ways to exert materials’ functionalities beyond the thermodynamic limit. The search for coherent phenomena has been a central topic in chemical physics although their direct characterization is often elusive. Here, we highlight recent advances in time-resolved x-ray absorption spectroscopy (tr-XAS) to investigate coherent phenomena, especially those that utilize the eminent light source of isolated attosecond pulses. The unparalleled time and state sensitivities of tr-XAS in tandem with the unique element specificity render the method suitable to study valence electronic dynamics in a wide variety of materials. The latest studies have demonstrated the capabilities of tr-XAS to characterize coupled electronic–structural coherence in small molecules and coherent light–matter interactions of core-excited excitons in solids. Furthermore, we address current opportunities and challenges in the exploration of coherent phenomena, with potential applications for energy- and bio-related systems, potential crossings, strongly driven solids, and quantum materials, and so with the ongoing developments in both theory and light sources, tr-XAS holds great promise for revealing the role of coherences in chemical dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multi-delay coherence imaging spectroscopy optimized for ion temperature measurements in the divertor plasma of the Wendelstein 7-X stellarator

A new coherence imaging spectroscopy (CIS) diagnostic optimized to measure the C 2+ impurity ion temperature T i spatial distribution in the divertor plasma of the W7-X stellarator is designed, tested, and validated. Using CIS to obtain T i in the edge of magnetically confined plasmas has historically been challenging because Doppler broadening and Zeeman splitting have comparable effects on the shape of spectral emission lines. To distinguish between these two mechanisms, a novel approach to birefringent crystal design is employed to minimize the diagnostic’s sensitivity to Zeeman splitting. The recently developed pixelated multi-delay CIS approach is also used to obtain four times as much spectral information as traditional CIS approaches. The T i -optimized CIS diagnostic is validated in a long-pulse W7-X plasma by comparison with a high-resolution spectrometer whose sightlines overlap with the CIS field of view. The CIS and spectrometer T i profiles have the same shape and agree to within 10% on average and 25% in the worst case. Images of the T i distribution near the divertor show toroidally elongated bands aligned with the magnetic field, with T i ranging between 10 and 40 eV.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Observation of room-temperature charge density wave correlations via coherent phonon spectroscopy in the Sn-doped kagome superconductor CsV 3 ⁢Sb 5

In this study, we perform ultrafast time-resolved reflectivity measurements to track the evolution of charge density wave (CDW) correlations in Sn-doped Kagome superconductor CsV 3⁢ Sb 5−𝑥 ⁢Sn 𝑥 . By extracting the coherent phonon spectrum, we evidence robust signatures of CDW correlations at temperature and doping ranges far beyond the phase boundary of long-range CDW order. Remarkably, we show that short-range CDW correlations survive up to room temperature in 𝑥 = 0.32 Sn-doped CsV 3 ⁢Sb 5 , supported by synchrotron x-ray diffraction measurements. We point out that the introduction of quenched disorder by Sn doping can pin the CDW and form static short-range CDW, which can explain the observed persistent CDW signatures. Our results thus corroborate the ubiquity and robustness of CDW correlations in Sn-doped CsV 3⁢ Sb 5 and provide new insights on the role of disorders on the CDW correlations in AV 3 ⁢Sb 5 family.

Charge density waves↗

An Exact Expression for Multidimensional Spectroscopy of a Spin‐Boson Hamiltonian

Multidimensional coherent spectroscopy is a powerful tool to characterize nonlinear optical response functions. Typically, multidimensional spectra are interpreted via a perturbative framework that straightforwardly provides intuition into the density matrix dynamics that give rise to specific spectral features. When the goal is to characterize system coupling to a thermal bath however, the perturbative formalism becomes unwieldy and yields less intuition. Here, an approach developed by Vagov et al. is extended to provide an exact expression for multidimensional spectra of a spin-boson Hamiltonian up to arbitrary order of electric field interaction. Furthermore, the utility of this expression is demonstrated by modeling polaron formation and coherent exciton-phonon coupling in quantum dots, which strongly agree with experiment.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nonlocal Coherent Optical Nonlinearities of a Macroscopic Quantum System

The optical responses of solids are typically understood to be local in space. Whether locality holds for the optical response of a macroscopic quantum system has, however, been largely unexplored. Here, we use multidimensional coherent spectroscopy at the optical diffraction limit to demonstrate nonlocal optical nonlinearities in a semiconductor microcavity. In conclusion, these nonlocal optical responses are both coherent and quantum in nature, deriving from the macroscopic length scale of confined exciton-polariton wave functions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A machine learning photon detection algorithm for coherent x-ray ultrafast fluctuation analysis

X-ray free electron laser experiments have brought unique capabilities and opened new directions in research, such as creating new states of matter or directly measuring atomic motion. One such area is the ability to use finely spaced sets of coherent x-ray pulses to be compared after scattering from a dynamic system at different times. This enables the study of fluctuations in many-body quantum systems at the level of the ultrafast pulse durations, but this method has been limited to a select number of examples and required complex and advanced analytical tools. By applying a new methodology to this problem, we have made qualitative advances in three separate areas that will likely also find application to new fields. As compared to the “droplet-type” models, which typically are used to estimate the photon distributions on pixelated detectors to obtain the coherent x-ray speckle patterns, our algorithm achieves an order of magnitude speedup on CPU hardware and two orders of magnitude improvement on GPU hardware. We also find that it retains accuracy in low-contrast conditions, which is the typical regime for many experiments in structural dynamics. Finally, it can predict photon distributions in high average-intensity applications, a regime which up until now has not been accessible. Our artificial intelligence-assisted algorithm will enable a wider adoption of x-ray coherence spectroscopies, by both automating previously challenging analyses and enabling new experiments that were not otherwise feasible without the developments described in this work.

47 OTHER INSTRUMENTATION↗

Spin–vibronic coherence drives singlet–triplet conversion

Design-specific control over the transitions between excited electronic states with different spin multiplicities is of the utmost importance in molecular and materials chemistry. Previous studies have indicated that the combination of spin-orbit and vibronic effects, collectively termed the spin-vibronic effect, can accelerate quantum-mechanically forbidden transitions at non-adiabatic crossings. However, it has been difficult to identify precise experimental manifestations of the spin-vibronic mechanism. Here we present coherence spectroscopy experiments that reveal the interplay between the spin, electronic and vibrational degrees of freedom that drive efficient singlet-triplet conversion in four structurally related dinuclear Pt(II) metal-metal-to-ligand charge-transfer (MMLCT) complexes. Photoexcitation activates the formation of a Pt-Pt bond, launching a stretching vibrational wavepacket. The molecular-structure-dependent decoherence and recoherence dynamics of this wavepacket resolve the spin-vibronic mechanism. Further, we find that vectorial motion along the Pt-Pt stretching coordinates tunes the singlet and intermediate-state energy gap irreversibly towards the conical intersection and subsequently drives formation of the lowest stable triplet state in a ratcheting fashion. This work demonstrates the viability of using vibronic coherences as probes to clarify the interplay among spin, electronic and nuclear dynamics in spin-conversion processes, and this could inspire new modular designs to tailor the properties of excited states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗