Coherent Two-dimensional Spectroscopy Research Articles

Detuning dependence of Rabi oscillations in an InAs self-assembled quantum dot ensemble

Inhomogeneous broadening in ensembles of semiconductor quantum dots (QDs) has hindered coherent operations due to the detuning effects, caused by the large fluctuation in the QD transition energy due to size dispersion. This difficulty is especially evident when using femtosecond laser pulses for excitation. Here, the authors successfully measure detuning-dependent coherent evolution for a QD ensemble by employing prepulse two-dimensional coherent spectroscopy. The dephasing mechanism is found to be significantly different from that observed using picosecond lasers. This work presents a novel method to explore collective phenomena, such as superfluorescence, as well as motivating future studies of coherent interactions in the femtosecond regime.

Stable biexcitons in two-dimensional metal-halide perovskites with strong dynamic lattice disorder

With strongly bound and stable excitons at room temperature, single-layer, two-dimensional organic-inorganic hybrid perovskites are viable semiconductors for light-emitting quantum optoelectronics applications. In such a technological context, it is imperative to comprehensively explore all the factors --- chemical, electronic and structural --- that govern strong multi-exciton correlations. Here, by means of two-dimensional coherent spectroscopy, we examine excitonic many-body effects in pure, single-layer (PEA)$_2$PbI$_4$ (PEA = phenylethylammonium). We determine the binding energy of biexcitons --- correlated two-electron, two-hole quasiparticles --- to be $44 \pm 5$\,meV at room temperature. The extraordinarily high values are similar to those reported in other strongly excitonic two-dimensional materials such as transition-metal dichalchogenides. Importantly, we show that this binding energy increases by $\sim25$\% upon cooling to 5\,K. Our work highlights the importance of multi-exciton correlations in this class of technologically promising, solution-processable materials, in spite of the strong effects of lattice fluctuations and dynamic disorder.

Classical coherent two-dimensional vibrational spectroscopy.

Two-dimensional (2D) ultrafast spectroscopy is a powerful tool for studying the electronic and vibrational structures of complex systems. Unfortunately, the physical interpretation of these experiments is obscured by conceptual problems in classical response theory, i.e., the divergence of classical nonlinear response functions. We demonstrate that these difficulties are avoided by modeling classical 2D experiments nonperturbatively, illustrating that nonlinear spectroscopy and nonlinear response are not synonymous. Numerical simulations allow a direct comparison between classical and quantum 2D spectra for simple, weakly anharmonic systems relevant to vibrational spectroscopy. We find that nonperturbative classical theory-although differing in quantitative details-accurately captures the key qualitative features of the quantum 2D spectrum, including the separation of the signal into wavevector-selected pathways, formation of cross peaks between coupled vibrational modes, and coherent beating in the signal as a function of waiting time (so-called "quantum beats"). These results are discussed in terms of a simple analytical model which captures the key physical features of classical 2D spectroscopy and provides a link between classical and quantum descriptions. One interesting conclusion from this comparison is that the "coherence" observed in ultrafast spectroscopy may (at least in vibrational experiments) be understood as a purely classical phenomenon, without reference to quantum mechanics.

Simplified expressions that incorporate finite pulse effects into coherent two-dimensional optical spectra

We derive general expressions that incorporate finite pulse envelope effects into a coherent two-dimensional optical spectroscopy (2DOS) technique. These expressions are simpler and less computationally intensive than the conventional triple integral calculations needed to simulate 2DOS spectra. The simplified expressions involving multiplications of arbitrary pulse spectra with 2D spectral response function are shown to be exactly equal to the conventional triple integral calculations of 2DOS spectra if the 2D spectral response functions do not vary with population time. With minor modifications, they are also accurate for 2D spectral response functions with quantum beats and exponential decay during population time. These conditions cover a broad range of experimental 2DOS spectra. For certain analytically defined pulse spectra, we also derived expressions of 2D spectra for arbitrary population time dependent 2DOS spectral response functions. Having simpler and more efficient methods to calculate experimentally relevant 2DOS spectra with finite pulse effect considered will be important in the simulation and understanding of the complex systems routinely being studied by using 2DOS.

Interpretation of optical three-dimensional coherent spectroscopy

As an extension to powerful two-dimensional coherent spectroscopy, optical three-dimensional (3D) coherent spectroscopy has been experimentally implemented and found beneficial in studying various systems in physics and chemistry. A critical challenge is how to interpret 3D spectra and extract useful quantitative information, given the richness and complexity of 3D data. Here, we demonstrate how the information of a system's optical response is manifested in 3D spectra by theoretical simulations of a few representative examples including a homogeneous three-level V system, an inhomogeneous three-level V system, and an inhomogeneous three-level ladder system. These examples show that important parameters of the system can be extracted from the spectral pattern, peak positions, amplitudes, and line shapes. The method developed here can be used to analyze 3D spectra of more sophisticated systems which might be a generalization or combination of the three examples, contributing to develop a general approach for the interpretation of 3D spectra.

Two-dimensional coherent spectroscopy of a THz quantum cascade laser: observation of multiple harmonics

Two-dimensional spectroscopy is performed on a terahertz (THz) frequency quantum cascade laser (QCL) with two broadband THz pulses. Gain switching is used to amplify the first THz pulse and the second THz pulse is used to probe the system. Fourier transforms are taken with respect to the delay time between the two THz pulses and the sampling time of the THz probe pulse. The two-dimensional spectrum consists of three peaks at (ωτ = 0, ωt = ω0), (ωτ = ω0, ωt = ω0), and (ωτ = 2ω0, ωt = ω0) where ω0 denotes the lasing frequency. The peak at ωτ = 0 represents the response of the probe to the zero-frequency (rectified) component of the instantaneous intensity and can be used to measure the gain recovery.

Formation of Ligno-Polyols: Fact or Fiction

The physical and chemical characteristics of several lignin-polyol blends were investigated by qualitative and quantitative methods from the view of biobased polyurethane applications. Four differently isolated biomass lignins from forestry and agricultural residues were blended with polyester polyol, and one was blended with polyethylene glycol. The isolated products were examined thoroughly to elucidate the subsequent lignin and polyol interactions during the premixing stage of biobased polyurethane formulation. Polyol was detected in lignin even after vigorous washings with several organic solvents and Soxhlet extraction. The experimental data coupled with two-dimensional heteronuclear multiple quantum coherence (HMQC) and nuclear magnetic resonance (NMR) spectroscopy confirmed the formation of ligno-polyols via strong intermolecular attractions, as well as some linkages between several lignin hydroxyl and polyol functional groups.

Neutral and charged inter-valley biexcitons in monolayer MoSe2

In atomically thin transition metal dichalcogenides (TMDs), reduced dielectric screening of the Coulomb interaction leads to strongly correlated many-body states, including excitons and trions, that dominate the optical properties. Higher-order states, such as bound biexcitons, are possible but are difficult to identify unambiguously using linear optical spectroscopy methods. Here, we implement polarization-resolved two-dimensional coherent spectroscopy (2DCS) to unravel the complex optical response of monolayer MoSe2 and identify multiple higher-order correlated states. Decisive signatures of neutral and charged inter-valley biexcitons appear in cross-polarized two-dimensional spectra as distinct resonances with respective ∼20 and ∼5 meV binding energies—similar to recent calculations using variational and Monte Carlo methods. A theoretical model considering the valley-dependent optical selection rules reveals the quantum pathways that give rise to these states. Inter-valley biexcitons identified here, comprising of neutral and charged excitons from different valleys, offer new opportunities for developing ultrathin biexciton lasers and polarization-entangled photon sources.

Observation of bound and antibound states of two excitons in GaAs single quantum well by two-dimensional coherent spectroscopy

Observation of bound and antibound states of two excitons in GaAs single quantum well by two-dimensional coherent spectroscopy

Excitonic coupling dominates the homogeneous photoluminescence excitation linewidth in semicrystalline polymeric semiconductors

We measure the homogeneous excitation linewidth of regioregular poly(3-hexylthiophene), a model semicrystalline polymeric semiconductor, by means of two-dimensional coherent photoluminescence excitation spectroscopy. At a temperature of 8\,K, we find a linewidth that is always $\gtrsim 110$\,meV full-width-at-half-maximum, which is a significant fraction of the total linewidth. It displays a spectral dependence and is minimum near the 0--0 origin peak. We interpret this spectral dependence of the homogeneous excitation linewidth within the context of a weakly coupled aggregate model.

Fragment Binding to β-Secretase 1 without Catalytic Aspartate Interactions Identified via Orthogonal Screening Approaches.

An approach to identify β-secretase 1 (BACE1) fragment binders that do not interact with the catalytic aspartate dyad is presented. A ThermoFluor (thermal shift) and a fluorescence resonance energy transfer enzymatic screen on the soluble domain of BACE1, together with a surface plasmon resonance (SPR) screen on the soluble domain of BACE1 and a mutant of one catalytic Asp (D32N), were run in parallel. Fragments that were active in at least two of these assays were further confirmed using one-dimensional NMR (WaterLOGSY) and SPR binding competition studies with peptidic inhibitor OM99-2. Protein-observed NMR (two-dimensional 15N heteronuclear single-quantum coherence spectroscopy) and crystallographic studies with the soluble domain of BACE1 identified a unique and novel binding mode for compound 12, a fragment that still occupies the active site while not making any interactions with catalytic Asps. This novel approach of combining orthogonal fragment screening techniques, for both wild-type and mutant enzymes, as well as binding competition studies could be generalized to other targets to overcome undesired interaction motifs and as a hit-generation approach in highly constrained intellectual property space.

Coherent two-dimensional spectroscopy of a Fano model

The Fano lineshape arises from the interference of two excitation pathways to reach a continuum. Its generality has resulted in a tremendous success in explaining the lineshapes of many one-dimensional spectroscopies - absorption, emission, scattering, conductance, photofragmentation - applied to very varied systems - atoms, molecules, semiconductors and metals. Unravelling a spectroscopy into a second dimension reveals the relationship between states in addition to decongesting the spectra. Femtosecond-resolved two-dimensional electronic spectroscopy (2DES) is a four-wave mixing technique that measures the time-evolution of the populations, and coherences of excited states. It has been applied extensively to the dynamics of photosynthetic units, and more recently to materials with extended band-structures. In this letter, we solve the full time-dependent third-order response, measured in 2DES, of a Fano model and give the new system parameters that become accessible.

Coherent Control of the Exciton-Biexciton System in an InAs Self-Assembled Quantum Dot Ensemble.

Coherent control of a strongly inhomogeneously broadened system, namely, InAs self-assembled quantum dots, is demonstrated. To circumvent the deleterious effects of the inhomogeneous broadening, which usually masks the results of coherent manipulation, we use prepulse two-dimensional coherent spectroscopy to provide a size-selective readout of the ground, exciton, and biexciton states. The dependence on the timing of the prepulse is due to the dynamics of the coherently generated populations. To further validate the results, we performed prepulse polarization dependent measurements and confirmed the behavior expected from selection rules. All measured spectra can be excellently reproduced by solving the optical Bloch equations for a 4-level system.

Polarization-dependent exciton linewidth in semiconductor quantum wells: A consequence of bosonic nature of excitons

The exciton coherent signal decay rate in GaAs quantum wells, as measured in four-wave mixing experiments, depends on the polarization of the excitation pulses. Using polarization-dependent two-dimensional coherent spectroscopy, we show that this behavior is due to the bosonic character of excitons. Interference between two different quantum mechanical pathways results in a smaller decay rate for cocircular and colinear polarization of the optical excitation pulses. This interference does not exist for cross-linearly polarized excitation pulses resulting in a larger decay rate. Our result shows that the bosonic nature of excitons must be considered when interpreting ultrafast spectroscopic studies of exciton dephasing in semiconductors. This behavior should be considered while interpreting results of ultrafast spectroscopy experiments involving bosonlike excitations.

Coherent and Incoherent Coupling Dynamics between Neutral and Charged Excitons in Monolayer MoSe2

The optical properties of semiconducting transition metal dichalcogenides are dominated by both neutral excitons (electron-hole pairs) and charged excitons (trions) that are stable even at room temperature. While trions directly influence charge transport properties in optoelectronic devices, excitons may be relevant through exciton-trion coupling and conversion phenomena. In this work, we reveal the coherent and incoherent nature of exciton-trion coupling and the relevant time scales in monolayer MoSe2 using optical two-dimensional coherent spectroscopy. Coherent interaction between excitons and trions is definitively identified as quantum beating of cross peaks in the spectra that persists for a few hundred femtoseconds. For longer times up to 10 ps, surprisingly, the relative intensity of the cross peaks increases, which is attributed to incoherent energy transfer likely due to phonon-assisted up-conversion and down-conversion processes that are efficient even at cryogenic temperature.

Solvent-induced polarization dynamics and coherent two-dimensional spectroscopy: Dissipaton equation of motion approach

This work exploits the dissipaton equation of motion (DEOM) approach to study the solvent-induced non-Condon polarization dynamics and its two-dimensional coherent spectroscopy for model excitonic systems. DEOM is a second quantization generation of the celebrated hierarchical equations of motion theory, with the capability of accurate evaluation for both reduced system and hybrid bath dynamics. The underlying dissipaton algebra includes the generalized Wick’s theorem and DEOM-space techniques for hybrid bath dynamics. Methods discussed also involve an efficient derivative–resum level truncation scheme that preserves the prescription invariance, and the mixed Heisenberg–Schrödinger picture approach for efficient simulation of nonlinear response functions. Our model simulations show clearly the correlated system-and-bath interference and the resulting Fano entanglement spectroscopy profiles.

Probing polaron excitation spectra in organic semiconductors by photoinduced-absorption-detected two-dimensional coherent spectroscopy

We report a theoretical description and experimental implementation of a novel two-dimensional coherent excitation spectroscopy based on quasi-steady-state photoinduced absorption measurement of a long-lived nonlinear population. We have studied a semiconductor-polymer:fullerene-derivative distributed heterostructure by measuring the 2D excitation spectrum by means of photoluminescence, photocurrent and photoinduced absorption from metastable polaronic products. We conclude that the photoinduced absorption probe is a viable and valuable probe in this family of 2D coherent spectroscopies.

Quantifying spectral diffusion by the direct measurement of the correlation function for excitons in semiconductor quantum wells

The phenomenon of spectral diffusion is common to a variety of inhomogeneously broadened systems. Spectral diffusion can be quantified through the frequency–frequency correlation function (FFCF), which is often approximated using observables from a variety of experimental techniques. We present a direct measurement of the temperature-dependent FFCF for excitons in semiconductor quantum wells using two-dimensional coherent spectroscopy. This technique enables the FFCF to be quantified without making any assumptions of the FFCF dynamics. Our results show that the Gauss–Markov approximation, which assumes exponential decay dynamics of the FFCF, is only valid for sample temperatures above 50 K. We compare our results with those obtained by the ellipticity and center-line slope measurements.

The role of the dipolar neighborhood on the relaxation dynamics of multichromophoric merocyanines.

The interactions between different chromophores within a molecular system are crucial to comprehend relaxation dynamics, regardless if one deals with small molecules or larger systems like polymers or aggregates. We investigate a series of merocyanine molecules that contain one, two or three highly dipolar (μg = 13.1 D) dyes in close vicinity to study the influence and origin of interactions, e.g., electronic, vibronic, or the formation of excitons. Relaxation dynamics are probed via transient absorption and coherent two-dimensional spectroscopy. Furthermore, we derive a general relaxation model which can be applied for all merocyanines under investigation and can be used as a reference point for other dipolar donor-acceptor dyes. The intramolecular charge-transfer state of the monomeric merocyanine is stabilized by dipolar neighbor molecules in the bis- and tris-chromophoric dyes.

Two-dimensional spectroscopy: An approach to distinguish Förster and Dexter transfer processes in coupled nanostructures

The linear and two-dimensional coherent optical spectra of Coulomb-coupled quantum emitters are discussed with respect to the underlying coupling processes. We present a theoretical analysis of the two different resonance energy transfer mechanisms between coupled nanostructures: F\"orster and Dexter interaction. Our investigation shows that the features visible in optical spectra of coupled quantum dots can be traced back to the nature of the underlying coupling mechanism (F\"orster or Dexter). Therefore, we discuss how the excitation transfer pathways can be controlled by choosing particular laser polarizations and mutual orientations of the quantum emitters in coherent two-dimensional spectroscopy. In this context, we analyze to what extent the delocalized double-excitonic states are bound to the optical selection rules of the uncoupled system.