Two-dimensional coherent spectroscopy (2DCS) probes the nonlinear optical response of correlated systems. An interesting application is the study of fractionalized excitations, which are challenging to distinguish unambiguously in linear response. Here we demonstrate how the sensitivity of optical matrix elements to variations in the photon polarization allows one to probe different aspects of low-lying excitations in models of the candidate fractionalized materials Ce 2 Zr 2 O 7 and Nd 2 Zr 2 O 7 , which host effective one-dimensional spin chains when subjected to a [110] magnetic field. We show how both fractionalized spinon excitations or conventional magnons can be picked out in the 2DCS response and how the response from polarized spin chains can be used to probe the dipolar-octupolar mixing angle θ through the relative intensity of one- and two-magnon signals. Further, we find that a [001] polarization of the probe field is particularly sensitive to lower band edge of the spinon continuum and can be used as a measure of the proximity of a quantum critical point in Ce 2 Zr 2 O 7 . 2DCS can thus be employed to provide invaluable and detailed information both on the constituent degrees of freedom of a quantum material and on their collective behavior. Published by the American Physical Society 2024
Two-dimensional coherent spectroscopy (2DCS) probes the nonlinear optical response of correlated systems. An interesting application is the study of fractionalized excitations, which are challenging to distinguish unambiguously in linear response. Here we demonstrate how the sensitivity of optical matrix elements to variations in the photon polarization allows one to probe different aspects of low-lying excitations in models of the candidate fractionalized materials Ce 2 Zr 2 O 7 and Nd 2 Zr 2 O 7 , which host effective one-dimensional spin chains when subjected to a [110] magnetic field. We show how both fractionalized spinon excitations or conventional magnons can be picked out in the 2DCS response and how the response from polarized spin chains can be used to probe the dipolar-octupolar mixing angle θ through the relative intensity of one- and two-magnon signals. Further, we find that a [001] polarization of the probe field is particularly sensitive to lower band edge of the spinon continuum and can be used as a measure of the proximity of a quantum critical point in Ce 2 Zr 2 O 7 . 2DCS can thus be employed to provide invaluable and detailed information both on the constituent degrees of freedom of a quantum material and on their collective behavior. Published by the American Physical Society 2024
Abstract With recent advances in terahertz (THz) sources and detection, two-dimensional coherent spectroscopy (2DCS), which allows one to probe nonlinear responses, now reaches the meV regime relevant for quasiparticle excitations in magnetic materials. This opens a promising route to reveal many-body phenomena that evade linear-response probes. To date, most experimental applications have focused on classical magnets, and a solid demonstration in a quantum magnet has yet to be established. Here we present a theoretical study of 2DCS in CoNb 2 O 6 , a quasi-one-dimensional Ising magnet that is believed to host fractionalized spinons which at low temperatures are confined by weak interchain coupling. Our analysis, which builds on an experimentally constrained effective S = 1/2 Hamiltonian, is found to reveal unambiguous 2DCS signatures of spinon deconfinement above the low-temperature ordered phase. Using a four-spinon approximation, we track these 2DCS signatures by sequentially building a faithful microscopic model for CoNb 2 O 6 , starting from the exactly solvable one-dimensional transverse-field Ising model (1 d TFIM) and successively adding additional interactions. In particular, adding a bond-dependent staggered YZ interaction to the 1 d -TFIM already reproduces many key spectral features of the full material Hamiltonian. Within this TFIM+YZ model, we find a series of bound states, including a four-spinon bound state that is distinct from the familiar two-spinon bound states. We further find that introducing a confinement potential suppresses sharp spinon-echo features, which are thought to reflect an underlying continuum of fractionalized excitations. Our results provide concrete predictions for future THz 2DCS experiments on CoNb 2 O 6 and related quasi-one-dimensional quantum magnets.
Two-dimensional coherent spectroscopy (2DCS) is an established method for characterizing molecules and has been proposed in the terahertz regime as a tool for probing exotic excitations of quantum magnets; however, the precise nature of the coupling between pump field and spin degrees of freedom has remained unclear. Here, we develop a general response theory of 2DCS and show how magnetoelectric as well as polarization couplings contribute to 2DCS in addition to the typically assumed magnetization. We propose experimental protocols to probe the presence of polarization couplings, for instance, from exchange-striction or spin-current mechanism, when the electric field couples to quadratic terms in spin operators. We provide example calculations for the paradigmatic twisted Kitaev chain material CoNb 2 O 6 and highlight the crucial role of contributions from cross-coupling between polarization and magnetic nonlinear susceptibilities. Our work paves the way for systematic studies of light-matter couplings in quantum magnets and for establishing 2DCS as a versatile tool for probing fractional excitations of exotic magnetic quantum phases.
Identifying quantum spin liquids, magnon breakdown, or fractionalized excitations in quantum magnets is an ongoing challenge due to the ambiguity in interpreting excitation continua occurring in linear-response probes. Recently, it was proposed that techniques measuring higher-order response, such as two-dimensional coherent spectroscopy (2DCS), could resolve such ambiguities. Numerically simulating nonlinear response functions can, however, be computationally very demanding. We present an efficient Lanczos-based method to compute second-order susceptibilities χ 2 ( ω t , ω τ ) directly in the frequency domain. Applying this to extended Kitaev models describing α − RuCl 3 , we find qualitatively different nonlinear responses between intermediate magnetic field strengths and the high-field regime. To put these results into context, we derive the general 2DCS response of partially polarized magnets within the linear spin-wave approximation, establishing that χ 2 ( ω t , ω τ ) is restricted to a distinct universal form if the excitations are conventional magnons. Deviations from this form, as predicted in our Lanczos-based simulations for α − RuCl 3 , can hence serve in 2DCS experiments as direct criteria to determine whether an observed excitation continuum is of conventional two-magnon type or of different nature.
Local moments with a spin S>1/2 can exhibit a rich variety of elementary quasiparticle excitations, such as quadrupolar excitations, that go beyond the dipolar magnons of conventional spin-1/2 systems. However, the experimental observation of such quadrupolar excitations is often challenging due to the dipolar selection rules of many linear response probes, rendering them invisible. Here we show that nonlinear spectroscopy, in the form of two-dimensional coherent spectroscopy (2DCS), can be used to reveal quadrupolar excitations. Considering a family of spin-1 Heisenberg ferromagnets with single-ion easy-axis anisotropy as an example, we explicitly calculate their 2DCS signature by combining exact diagonalization and generalized spin wave theory. We further demonstrate that 2DCS can provide access to the quadrupolar weight of an excitation, analogous to how linear response provides access to the dipolar weight. Our work highlights the potential of nonlinear spectroscopy as a powerful tool to diagnose multipolar excitations in quantum magnets.
Two-dimensional coherent spectroscopy (2DCS) with terahertz radiation offers a promising new avenue for the exploration of many-body phenomena in quantum magnets. This includes the potential diagnosis of fractionalized excitations, for which linear response often struggles due to the indistinguishability of a continuum of fractional excitations from that caused by disorders or impurities. However, the interpretation of the complex results produced by 2DCS remains a challenge. Here, we explore a numerical approach based on exact diagonalization (ED) to help push forward our understanding of 2DCS and, as an example, use it to study the impact of confinement in the one-dimensional transverse field Ising (TFIM) model. We first validate our approach by comparing numerical ED and exact analytical results for the spectroscopic signatures of fractionalized spinons in the model, which exhibits a sharp spinon-echo signal in 2DCS, and show how to understand the finite-size effects inevitable with the inherently small system sizes in ED calculations. By augmenting the model with a longitudinal field, which breaks integrability and introduces confinement of spinon pairs, we observe significant changes to the 2DCS spectrum, such as nonsymmetric broadening of the spinon-echo signal. To further elucidate these changes, we introduce a ``four-kink'' approximation, an effective model that captures the interactions between multiple (confined) spinon pairs. Comparing ED data to these four-kink results provides understanding of the multiple features of the 2DCS spectra, allowing us to interpolate between finite-system size data and the thermodynamic limit. One advantage of our ED approach is its possible extension to finite temperatures, which we explore using thermally pure quantum states and demonstrate how the intensity and spectroscopic patterns of 2DCS change when going beyond the integrable model. Our numerically exact results provide a benchmark for future experiments and theoretical studies relying on approximation methods and pave the way for the exploration of fractionalized excitations in quantum magnets.
Two-dimensional coherent terahertz spectroscopy (2DCS) emerges as a valuable tool to probe the nature, couplings, and lifetimes of excitations in quantum materials. It thus promises to identify unique signatures of spin liquid states in quantum magnets by directly probing properties of their exotic fractionalized excitations. Here, we calculate the second-order 2DCS of the Kitaev honeycomb model and demonstrate that distinct spin liquid fingerprints appear already in this lowest-order nonlinear response χyzx(2)(ω1,ω2) when using crossed light polarizations. We further relate the off-diagonal 2DCS peaks to the localized nature of the matter Majorana excitations trapped by Z2 flux excitations and show that 2DCS thus directly probes the inverse participation ratio of Majorana wavefunctions. By providing experimentally observable features of spin liquid states in the 2D spectrum, our work can guide future 2DCS experiments on Kitaev magnets.