Coherent Two-dimensional Spectroscopy Research Articles

Revealing Novel Aspects of Light-Matter Coupling by Terahertz Two-Dimensional Coherent Spectroscopy: The Case of the Amplitude Mode in Superconductors.

Recently developed terahertz (THz) two-dimensional coherent spectroscopy (2DCS) is a powerful technique to obtain materials information in a fashion qualitatively different from other spectroscopies. Here, we utilized THz 2DCS to investigate the THz nonlinear response of conventional superconductor NbN. Using broadband THz pulses as light sources, we observed a third-order nonlinear signal whose spectral components are peaked at twice the superconducting gap energy 2Δ. With narrow-band THz pulses, a THz nonlinear signal was identified at the driving frequency Ω and exhibited a resonant enhancement at temperature when Ω=2Δ. General theoretical considerations show that such a resonance can arise only from a disorder-activated paramagnetic coupling between the light and the electronic current. This proves that the nonlinear THz response can access processes distinct from the diamagnetic Raman-like density fluctuations, which are believed to dominate the nonlinear response at optical frequencies in metals. Our numerical simulations reveal that, even for a small amount of disorder, the Ω=2Δ resonance is dominated by the superconducting amplitude mode over the entire investigated disorder range. This is in contrast to other resonances, whose amplitude-mode contribution depends on disorder. Our findings demonstrate the unique ability of THz 2DCS to explore collective excitations inaccessible in other spectroscopies.

Microscopic many-body theory of two-dimensional coherent spectroscopy of exciton polarons in one-dimensional materials

Microscopic many-body theory of two-dimensional coherent spectroscopy of exciton polarons in one-dimensional materials

Extreme terahertz magnon multiplication induced by resonant magnetic pulse pairs

Nonlinear interactions of spin-waves and their quanta, magnons, have emerged as prominent candidates for interference-based technology, ranging from quantum transduction to antiferromagnetic spintronics. Yet magnon multiplication in the terahertz (THz) spectral region represents a major challenge. Intense, resonant magnetic fields from THz pulse-pairs with controllable phases and amplitudes enable high order THz magnon multiplication, distinct from non-resonant nonlinearities such as the high harmonic generation by below-band gap electric fields. Here, we demonstrate exceptionally high-order THz nonlinear magnonics. It manifests as 7th-order spin-wave-mixing and 6th harmonic magnon generation in an antiferromagnetic orthoferrite. We use THz two-dimensional coherent spectroscopy to achieve high-sensitivity detection of nonlinear magnon interactions up to six-magnon quanta in strongly-driven many-magnon correlated states. The high-order magnon multiplication, supported by classical and quantum spin simulations, elucidates the significance of four-fold magnetic anisotropy and Dzyaloshinskii-Moriya symmetry breaking. Moreover, our results shed light on the potential quantum fluctuation properties inherent in nonlinear magnons.

Unveiling Multiquantum Excitonic Correlations in Push-Pull Polymer Semiconductors.

Bound and unbound Frenkel-exciton pairs are essential transient precursors for a variety of photophysical and biochemical processes. In this work, we identify bound and unbound Frenkel-exciton complexes in an electron push-pull polymer semiconductor using coherent two-dimensional spectroscopy. We find that the dominant A0-1 peak of the absorption vibronic progression is accompanied by a subpeak, each dressed by distinct vibrational modes. By considering the Liouville pathways within a two-exciton model, the imbalanced cross-peaks in one-quantum rephasing and nonrephasing spectra can be accounted for by the presence of pure biexcitons. The two-quantum nonrephasing spectra provide direct evidence for unbound exciton pairs and biexcitons with dominantly attractive force. In addition, the spectral features of unbound exciton pairs show mixed absorptive and dispersive character, implying many-body interactions within the correlated Frenkel-exciton pairs. Our work offers novel perspectives on the Frenkel-exciton complexes in semiconductor polymers.

Molecular Polaritons for Chemistry, Photonics and Quantum Technologies.

Molecular polaritons are quasiparticles resulting from the hybridization between molecular and photonic modes. These composite entities, bearing characteristics inherited from both constituents, exhibit modified energy levels and wave functions, thereby capturing the attention of chemists in the past decade. The potential to modify chemical reactions has spurred many investigations, alongside efforts to enhance and manipulate optical responses for photonic and quantum applications. This Review centers on the experimental advances in this burgeoning field. Commencing with an introduction of the fundamentals, including theoretical foundations and various cavity architectures, we discuss outcomes of polariton-modified chemical reactions. Furthermore, we navigate through the ongoing debates and uncertainties surrounding the underpinning mechanism of this innovative method of controlling chemistry. Emphasis is placed on gaining a comprehensive understanding of the energy dynamics of molecular polaritons, in particular, vibrational molecular polaritons─a pivotal facet in steering chemical reactions. Additionally, we discuss the unique capability of coherent two-dimensional spectroscopy to dissect polariton and dark mode dynamics, offering insights into the critical components within the cavity that alter chemical reactions. We further expand to the potential utility of molecular polaritons in quantum applications as well as precise manipulation of molecular and photonic polarizations, notably in the context of chiral phenomena. This discussion aspires to ignite deeper curiosity and engagement in revealing the physics underpinning polariton-modified molecular properties, and a broad fascination with harnessing photonic environments to control chemistry.

Exciton-carrier coupling in a metal halide perovskite nanocrystal assembly probed by two-dimensional coherent spectroscopy

The surface chemistry and inter-connectivity within perovskite nanocrystals play a critical role in determining the electronic interactions. They manifest in the Coulomb screening of electron–hole correlations and the carrier relaxation dynamics, among other many-body processes. Here, we characterize the coupling between the exciton and free carrier states close to the band-edge in a ligand-free formamidinium lead bromide nanocrystal assembly via two-dimensional coherent spectroscopy. The optical signatures observed in this work show: (i) a nonlinear spectral lineshape reminiscent of Fano-like interference that evidences the coupling between discrete electronic states and a continuum, (ii) symmetric excited state absorption cross-peaks that suggest the existence of a coupled exciton-carrier excited state, and (iii) ultrafast carrier thermalization and exciton formation. Our results highlight the presence of coherent coupling between exciton and free carriers, particularly in the sub-100 femtosecond timescales.

Microscopic many-body theory of two-dimensional coherent spectroscopy of excitons and trions in atomically thin transition metal dichalcogenides

Microscopic many-body theory of two-dimensional coherent spectroscopy of excitons and trions in atomically thin transition metal dichalcogenides

Higher-Order Multidimensional and Pump-Probe Spectroscopies.

Transient absorption and coherent two-dimensional spectroscopy are widely established methods for the investigation of ultrafast dynamics in quantum systems. Conventionally, they are interpreted in the framework of perturbation theory at the third order of interaction. Here, we discuss the potential of higher-(than-third-)order pump-probe and multidimensional spectroscopy to provide insight into excited multiparticle states and their dynamics. We focus on recent developments from our group. In particular, we demonstrate how phase cycling can be used in fluorescence-detected two-dimensional spectroscopy to isolate higher-order spectra that provide information about highly excited states such as the correlation of multiexciton states. We discuss coherently detected fifth-order 2D spectroscopy and its power to track exciton diffusion. Finally, we show how to extract higher-order signals even from ordinary pump-probe experiments, providing annihilation-free signals at high excitation densities and insight into multiexciton interactions.

High-order pump-probe and high-order two-dimensional electronic spectroscopy on the example of squaraine oligomers.

Time-resolved spectroscopy is commonly used to study diverse phenomena in chemistry, biology, and physics. Pump-probe experiments and coherent two-dimensional (2D) spectroscopy have resolved site-to-site energy transfer, visualized electronic couplings, and much more. In both techniques, the lowest-order signal, in a perturbative expansion of the polarization, is of third order in the electric field, which we call a one-quantum (1Q) signal because in 2D spectroscopy it oscillates in the coherence time with the excitation frequency. There is also a two-quantum (2Q) signal that oscillates in the coherence time at twice the fundamental frequency and is fifth order in the electric field. We demonstrate that the appearance of the 2Q signal guarantees that the 1Q signal is contaminated by non-negligible fifth-order interactions. We derive an analytical connection between an nQ signal and (2n + 1)th-order contaminations of an rQ (with r < n) signal by studying Feynman diagrams of all contributions. We demonstrate that by performing partial integrations along the excitation axis in 2D spectra, we can obtain clean rQ signals free of higher-order artifacts. We exemplify the technique using optical 2D spectroscopy on squaraine oligomers, showing clean extraction of the third-order signal. We further demonstrate the analytical connection with higher-order pump-probe spectroscopy and compare both techniques experimentally. Our approach demonstrates the full power of higher-order pump-probe and 2D spectroscopy to investigate multi-particle interactions in coupled systems.

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. 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.

Revealing the structure and distribution changes of corn stalk lignin during the Organosolv Pretreatment

During the pretreatment of biomass, the research on the migration process of lignin in the cell wall and the change of chemical structure is very important for improving pretreatment and subsequent lignin upgrading. Hence, corn stalk lignin was extracted by 1, 4-dioxane organosolv system under mild conditions with varying pretreatment time and 0.1 M hydrochloric acid as catalyst. The heterogeneity of lignin removal in the different morphological areas of the cell wall was revealed by advanced imaging techniques. Results indicated that during the pretreatment with dioxane organosolv, the removal of lignin started from the secondary wall of the cell wall, and gradually developed outward to the compound middle lamella. Meanwhile, the resulting lignin obtained through different pretreatment times was characterized by two-dimensional heteronuclear single quantum coherence spectroscopy (2D-HSQC) and gel permeation chromatography (GPC). These characterization results indicated that there were more syringyl (S) units in the lignin that were removed first, and the proportion of guaiacyl (G) units was increased as the pretreatment continued. All the evidence supports the idea that the main reason for the significant differences in lignin structures at various periods of the lignin removal process is that the lignin come from different cell wall regions.

Two-dimensional coherent spectroscopy of trion-polaritons and exciton-polaritons in atomically thin transition metal dichalcogenides

We present a microscopic many-body calculation of the nonlinear two-dimensional coherent spectroscopy (2DCS) of trion-polaritons and exciton-polaritons in charge-tunable transition-metal-dichalcogenides monolayers placed in an optical microcavity. The charge tunability leads to an electron gas with nonzero density that brings brightness to the trion — a polaron quasiparticle formed by an exciton with a nonzero residue bounded to the electron gas. As a result, a trion-polariton is created under strong light-matter coupling, as observed in the recent experiment by Sidler et al. [Nat. Phys. 13, 255 (2017)]. We analyze in detail the structure of trion-polaritons, by solving an extended Chevy ansatz for the trion quasiparticle wave-function. We confirm that the effective light-matter coupling for trion-polaritons is determined by the residue of the trion quasiparticle. The solution of the full many-body polaron states within Chevy ansatz enables us to microscopically calculate the nonlinear 2DCS spectrum of both trion-polaritons and exciton-polaritons. We predict the existence of three kinds of off-diagonal cross-peaks in the 2DCS spectrum, as an indication of the coherence among the different branches of trion-polaritons and exciton-polaritons. Due to the sensitivity of 2DCS spectrum to quasiparticle interactions, our work provides a good starting point to explore the strong nonlinearity exhibited by trion-polaritons in some recent exciton-polariton experiments.

Two-dimensional coherent spectrum of interacting spinons from matrix product states

We compute numerically the second- and third-order nonlinear magnetic susceptibilities of an Ising ladder model in the context of two-dimensional coherent spectroscopy by using the infinite time-evolving block decimation method. The Ising ladder model couples a quantum Ising chain to a bath of polarized spins, thereby effecting the decay of spinon excitations. We show that its third-order susceptibility contains a robust spinon echo signal in the weak-coupling regime, which appears in the two-dimensional coherent spectrum as a highly anisotropic peak on the frequency plane. The spinon echo peak reveals the dynamical properties of the spinons. In particular, the spectral peak corresponding to the high-energy spinons, which couple to the bath, is suppressed with increasing coupling, whereas those corresponding to low-energy spinons do not show any significant changes.

Nonlinear response of the Kitaev honeycomb lattice model in a weak magnetic field

We investigate the nonlinear response of the Kitaev honeycomb lattice model in a weak magnetic field using the theory of two-dimensional (2D) coherent spectroscopy. We observe that at the isotropic point in the non-Abelian phase of this model, the nonlinear spectrum in the 2D frequency domain consists of sharp signals that originate from the flux excitations and Majorana bound states. Signatures of different flux excitations can be clearly observed in this spectrum, such that one can observe evidences of flux states with 4-adjacent, 2-nonadjacent, and 4-far-separated fluxes, which are not visible in linear response spectroscopy such as neutron scattering experiments. Moreover, in the Abelian phase we perceive that the spectrum in the frequency domain is composed of streak signals. These signals, as in the nonlinear response of the pure Kitaev model, represent a distinct signature of itinerant Majorana fermions. However, deep in the Abelian phase whenever a Kitaev exchange coupling is much stronger than the others, the streak signals are weakened and only single sharp spots are seen in the response, which resembles the dispersionless response of the conventional toric code.

Pulse overlap ambiguities in multiple quantum coherence spectroscopy.

Coherent two-dimensional electronic spectroscopy probes ultrafast dynamics using femtosecond pulses. In the case where the time scale of the studied dynamics become comparable to the pulse duration, pulse overlap effects may compromise the experimental data. Here, we perform one-dimensional coherence scans and study pulse overlap effects in clean two-level systems. We find parasitic multiple-quantum coherences as a consequence of the arbitrary time ordering during the temporal pulse overlap. Surprisingly, the coherence lifetimes exceed the pulse coherence time by a factor of 1.85. These findings have important implications for the interpretation of higher-order coherent two-dimensional and related spectroscopy experiments.

Optical two-dimensional coherent spectroscopy of cold atoms.

We report an experimental demonstration of optical two-dimensional coherent spectroscopy (2DCS) in cold atoms. The experiment integrates a collinear 2DCS setup with a magneto-optical trap (MOT), in which cold rubidium (Rb) atoms are prepared at a temperature of approximately 200 µK and a number density of 1010 cm-3. With a sequence of femtosecond laser pulses, we first obtain one-dimensional second- and fourth-order nonlinear signals and then acquire both one-quantum and zero-quantum 2D spectra of cold Rb atoms. The capability of performing optical 2DCS in cold atoms is an important step toward optical 2DCS study of many-body physics in cold atoms and ultimately in atom arrays and trapped ions. Optical 2DCS in cold atoms/molecules can also be a new avenue to probe chemical reaction dynamics in cold molecules.

Identifying incoherent mixing effects in the coherent two-dimensional photocurrent excitation spectra of semiconductors.

We have previously demonstrated that in the context of two-dimensional (2D) coherent electronic spectroscopy measured by phase modulation and phase-sensitive detection, an incoherent nonlinear response due to pairs of photoexcitations produced via linear excitation pathways contributes to the measured signal as an unexpected background [Grégoire et al., J. Chem. Phys. 147, 114201 (2017)]. Here, we simulate the effect of such incoherent population mixing in the photocurrent signal collected from a GaAs solar cell by acting externally on the transimpedance amplifier circuit used for phase-sensitive detection, and we identify an effective strategy to recognize the presence of incoherent population mixing in 2D data. While we find that incoherent mixing is reflected by the crosstalk between the linear amplitudes at the two time-delay variables in the four-pulse excitation sequence, we do not observe any strict phase correlations between the coherent and incoherent contributions, as expected from modeling of a simple system.

Broadband optical two-dimensional coherent spectroscopy of a rubidium atomic vapor

Optical two-dimensional coherent spectroscopy (2DCS) has become a powerful tool for studying energy level structure, dynamics, and coupling in many systems including atomic ensembles. Various types of two-dimensional (2D) spectra, including the so-called single-quantum, zero-quantum, and double-quantum 2D spectra, of both D lines (D$_1$ and D$_2$ transitions) of potassium (K) atoms have been reported previously. For rubidium (Rb), a major difference is that the D-lines are about 15 nm apart as opposed to only about 3 nm for K. Simultaneously exciting both D-lines of Rb atoms requires a broader laser bandwidth for the experiment. Here, we report a broadband optical 2DCS experiment in an Rb atomic vapor. A complete set of single-quantum, zero-quantum, and double-quantum 2D spectra including both D-lines of Rb atoms were obtained. The experimental spectra were reproduced by simulated 2D spectra based on the perturbation solutions to the optical Bloch equations. This work in Rb atoms complements previous 2DCS studies of K and Rb with a narrower bandwidth that covers two D-lines of K or only a single D-line of Rb. The broadband excitation enables the capability to perform double-quantum and multi-quantum 2DCS of both D-lines of Rb to study many-body interactions and correlations in comparison with K atoms.

Observation of optical coherence in a disordered metal-molecule interface by coherent optical two-dimensional photoelectron spectroscopy

Coherent multidimensional optical spectroscopy methods overcome some of the limitations found in their one-dimensional counterparts and allow us, for example, to resolve overlapped spectral features, to separate homogeneous and inhomogeneous broadening, and to track the energy transfer kinetics and coherent dynamics in complex quantum systems. In their most common configurations, signal detection is achieved by optical means, making these techniques widespread in studies of bulk systems but less common in the surface and interface sciences. In this paper, we demonstrate an inherently surface-sensitive two-dimensional coherent spectroscopy scheme, based on photoelectron detection, by studying the interface formed between tris(8-hydroxyquinolinato)aluminium (${\mathrm{Alq}}_{3}$) and a ferromagnetic Co surface. Despite the inhomogeneous linewidth broadening (\ensuremath{\approx}800 meV) in the ensemble of disordered molecules, we resolve two narrow resonances (\ensuremath{\approx}10 meV linewidth) with an energy spacing of \ensuremath{\approx}80 meV. By combining experimental data and simulations, using the Lindblad master equation, we identify these resonances as lowest unoccupied molecular orbital (LUMO) to $\mathrm{LUMO}+1$ transitions in chemically decoupled second-layer ${\mathrm{Alq}}_{3}$ molecules and deduce related optical coherence lifetimes of at least 120 and 240 fs. These observations establish that ${\mathrm{Alq}}_{3}$ molecules in a disordered adsorbate layer exhibit well-defined and rather homogeneous internal electronic transitions, although the absolute energetic positions of the involved states with respect to the substrate reference are significantly affected by the disorder. The results indicate that inhomogeneous line broadening in a disordered ${\mathrm{Alq}}_{3}$ layer and pure dephasing have only a minor impact on optical transitions in individual molecules. This opens interesting opportunities for coherent control schemes and emphasizes the importance of optical coherences for all electron dynamics, even in disordered hybrid metal-molecule interfaces.

Measuring Exciton Fine-Structure in Randomly Oriented Perovskite Nanocrystal Ensembles Using Nonlinear Optical Spectroscopy: Theory.

Lead halide perovskite nanocrystals (PNCs) exhibit unique optoelectronic properties, many of which originate from a purported bright-triplet exciton fine-structure. A major impediment to measuring this fine-structure is inhomogeneous spectral broadening, which has limited most experimental studies to single-nanocrystal spectroscopies. It is shown here that the linearly polarized single-particle selection rules in PNCs are preserved in nonlinear spectroscopies of randomly oriented ensembles. Simulations incorporating rotational averaging demonstrate that techniques such as transient absorption and two-dimensional coherent spectroscopy are capable of resolving exciton fine-structure in PNCs, even in the presence of inhomogeneous broadening and orientation disorder.