Quantum Beats Research Articles

Vibronic coherent quantum beat in four-layer platinum carbonyl cluster.

Vibronic coherence has been studied for years, but direct comparisons between the rich experimental features and theory remain rare. In this work, we investigate the vibronic coherent quantum beat of a four-layer platinum carbonyl cluster [Pt3(CO)6]42- in a solution utilizing femtosecond vis-pump/vis-probe transient absorption spectroscopy. By varying the excitational wavelength, quantum beats coupled to either the electronic ground state or the excited state are selectively prepared. A 41cm-1 beat at the ground state with a phase flip at 615nm and a 28cm-1 beat at the excited state with a phase node at 735nm are observed. The beat amplitudes are asymmetric, stronger on the red side for ground state beats but weaker for excited state beats. Quantum chemistry calculations suggest that these beats result from coupling between the [Pt3(CO)6] layer motions and the electronic excitation. Theoretical model calculations for quantum beats at both electronic states are performed following the doorway-window approach. The calculations explain the oscillation frequency difference, the node positions, and the asymmetry. The beats with different frequencies result from vibronic coupling with different electronic states with the Herzberg-Teller (ground) or Franck-Condon term (excited) involved. The theoretical nodes occur at absorption and fluorescence centers, respectively, although experimental results show a slight blueshift. Quantum window operator calculations link the beat amplitude asymmetry to the Franck-Condon factor matrix imbalances, with the number of nodes dependent on the electronic dephasing rate. The theoretical insights for quantum beats are expected to be general, potentially helpful for the interpretation of observations in other systems.

Revealing and Manipulating Hidden Fine-Structure Coherence of Bright Excitons in CsPbI3 Perovskite Quantum Dots.

Observation and understanding of fine-structure splitting of bright excitons in lead halide perovskite quantum dots (QDs) are crucial to their emerging applications in quantum light sources and exciton coherence manipulation. Recent studies demonstrate that ensemble-level polarization-resolved transient absorption spectroscopy can reveal the quantum beats arising from the coherence between two fine-structure levels. Here we report the observation of an extra fine-structure quantum coherence hidden in previous studies by using cryo-magnetic quantum beat spectroscopy. In ∼6 nm CsPbI3 QDs, two splitting energies of 0.25 and 1.20 meV were observed at 1.7 K, which gradually increased to 0.74 and 1.55 meV, respectively, when a longitudinal magnetic field up to 7 T was applied. The field dependence allowed us to extract two distinct nominal Landé g-factors corresponding to QDs with different orientations with respect to the external field.

Temperature-dependent quantum beats between neutral and charged excitons in monolayer MoSe2

Temperature-dependent quantum beats between neutral and charged excitons in monolayer MoSe2

Decoherence-induced formation of sub-poissonian entangled and steerable states of collective fields

The decoherence process has a tendency to yield the evolution of a pure state into a mixed one and to cause the quantum-to-classical transition by the coupling of a system of interest to the reservoir with infinitely many degrees of freedom. This is the major obstacle to the implementation of quantum computation and hence the realization of quantum computers. We propose a scheme to create unconditionally sub-Poissonian entangled and steerable states of the collective cavity field modes by use of the dissipation process. Based on the suitable choice of combination modes, the scheme uses the inherent, efficient and controllable two-mode squeezed vacuum reservoir coupled to the combination modes of concern rather than the original cavity modes in the two-level quantum beat laser. The decoherence is shown to pull the collective modes into the sub-Poissonian entangled and steerable states in the stationary regime, while the job of the dissipation of the individual cavity fields is to give rise to the degradation of the bipartite entanglement of the two individual modes and to inhibit the occurrence of the quantum steering from one cavity mode to the other. In particular for the case that the external driving field is close to the exact resonance with the atom, the collective fields are eventually prepared asymptotically in the stationary Einstein–Podolsky–Rosen state, while the two individual cavity modes are pulled into the vacuum states and reach steady state. The disappearance of the decoherence disables the nonclassical states of the collective modes, while the ignorance of the dissipation process of the cavity field modes guarantees the generation of the entanglement between the pair of individual modes. The decoherence-induced formation of a nonclassical source is ascribed to the four-wave mixing process together with the intrinsic amplitude and phase locking.

Multilevel dynamics of matter waves scattering in finite potential wells

We explore the dynamics of matter wave scattering in finite potential wells using analytical solutions of the Schrödinger equation within the framework of a quantum shutter model. We find that the incident wave interferes with the bound states of the quantum well, resulting in time-domain oscillations. These oscillations exhibit Rabi-type frequencies, characterised by the energy differences between the incident wave and the bound states of the quantum well. We show that in systems with double-bound states, the interference pattern is characterised by quantum beats in the time-dependent probability density. The period of these beatings depends on the energy difference between the bound states, which can be tuned by controlling the potential parameters. In the general case where bound, anti-bound, and resonant states coexist in the system spectrum, complex oscillations in the probability density arise from the interactions of the incident wave with different quantum states. We demonstrate that the bound states sector can effectively describe this complex behaviour, providing a simple and reliable analytical expression for the probability density in multilevel systems. This formula highlights the significant role of bound states, whose interaction with the incident wave dominates the transient probability density. This contrasts with conventional systems with potential barriers and wells, where resonances govern the wave dynamics.

Persistence of Spin Coherence in a Crystalline Environment.

We analyze quantum interference in the triplet-exciton pair generated by singlet exciton fission in a molecular crystal and introduce transport-induced dephasing (TID) as a key effect that can suppress the expected fluorescence quantum beats when the triplet-exciton wave function can localize on inequivalent sites. TID depends on the triplet-exciton hopping rate between inequivalent sites and on the energy shifts among the stationary states of the entangled triplet pair in different spatial configurations. The theoretical model is confirmed by experiments in rubrene single crystals, where triplet pairs remain entangled for more than 50ns but quantum beats are suppressed by TID within a few nanoseconds when the magnetic field is misaligned by just a few degrees from specific symmetric directions. Our experiments deliver the zero-field parameters for the rubrene molecule in its orthorhombic lattice and information on triplet-exciton transport, in particular, the triplet-exciton hopping rate between inequivalent sites, which we evaluate to be of the order of 150ps in rubrene.

Optical Studies of Doped Two-Dimensional Lead Halide Perovskites: Evidence for Rashba-Split Branches in the Conduction Band.

Two-dimensional (2D) hybrid organic/inorganic perovskites are an emerging materials class for optoelectronic and spintronic applications due to strong excitonic absorption and emission, large spin-orbit coupling, and Rashba spin-splitting effects. For many of the envisioned applications, tuning the majority charge carrier (electron or hole) concentration is desirable, but electronic doping of metal-halide perovskites has proven to be challenging. Here, we demonstrate electron injection into the lower-energy branch of the Rashba-split conduction band of 2D phenethylammonium lead iodide by means of n-type molecular doping at room temperature. The molecular dopant, benzyl viologen (BV), is shown to compensate adventitious p-type impurities and can lead to a tunable Fermi level above the conduction band minimum and increased conductivity in intrinsic samples. The doping-induced carrier concentration is monitored by the observation of free-carrier absorption and intraband optical transitions in the infrared spectral range. These optical measurements allow for an estimation of the Rashba splitting energy ER ≈38 ± 4 meV. Photoinduced quantum beating measurements demonstrate that the excess electron density reduces the electron spin g-factor by ca. 6%. This work demonstrates controllable carrier concentrations in hybrid organic/inorganic perovskites and yields potential for room temperature spin control through the Rashba effect.

Coherent Transfer of Lattice Entropy via Extreme Nonlinear Phononics in Metal Halide Perovskites

Entropy transfer in metal halide perovskites, characterized by significant lattice anharmonicity and low stiffness, underlies the remarkable properties observed in their optoelectronic applications, ranging from solar cells to lasers. The conventional view of this transfer involves stochastic processes occurring within a thermal bath of phonons, where the lattice arrangement and energy flow from higher- to lower-frequency modes. Here, we unveil a comprehensive chronological sequence detailing a conceptually distinct coherent transfer of entropy in a prototypical perovskite CH3NH3Pbl3. The terahertz periodic modulation imposes vibrational coherence into electronic states, leading to the emergence of mixed (vibronic) quantum beat between approximately 3 and 0.3 THz. We highlight a well-structured bidirectional time-frequency transfer of these diverse phonon modes, each developing at different times and transitioning from high to low frequencies from 3 to 0.3 THz, before reversing direction and ascending to around 0.8 THz. First-principles molecular dynamics simulations disentangle a complex web of coherent-phononic coupling pathways and identify the salient roles of the initial modes in shaping entropy evolution at later stages. Capitalizing on coherent entropy transfer and dynamic anharmonicity presents a compelling opportunity to exceed the fundamental thermodynamic (Shockley-Queisser) limit of photoconversion efficiency and to pioneer novel optoelectronic functionalities. Published by the American Physical Society 2024

Core-Hole Coherent Spectroscopy in Molecules.

We study the ultrafast dynamics initiated by a coherent superposition of core-excited states of nitrous oxide molecule. Using high-level abinitio methods, we show that the decoherence caused by the electronic decay and the nuclear dynamics is substantially slower than the induced ultrafast quantum beatings, allowing the system to undergo several oscillations before it dephases. We propose a proof-of-concept experiment using the harmonic up-conversion scheme available at x-ray free-electron laser facilities to trace the evolution of the created core-excited-state coherence through a time-resolved x-ray photoelectron spectroscopy.

Analytical model for spin dynamics in radical pairs under the spin-locking condition.

Spin dynamics in triplet radical pairs are theoretically studied under the spin-locking condition, where singlet-triplet mixing is blocked by the resonant microwave field. A key assumption in the theory is simultaneous excitations of T+-T0 and T--T0 transitions in triplet radical pairs. This assumption allows for the application of a three-state model [Yago, J. Chem. Phys. 151, 214501 (2019)] to describe the spin dynamics of triplet radical pairs. The analysis based on the three-state model shows that the triplet states are quantized along the direction of a microwave-induced magnetic field (B1) in the rotating frame under the spin-locking condition. This gives rise to a new spin-locking phenomenon where T+-T0 and T--T0 mixing are most enhanced at magnetic fields that deviate from the resonance by ±B1. It is also shown that the quantum beats observed under the spin-locking condition originate from the spin dynamics in triplet radical pairs.

Highly-Polarized Emission Provided by Giant Optical Orientation of Exciton Spins in Lead Halide Perovskite Crystals.

Quantum technologic and spintronic applications require reliable material platforms that enable significant and long-living spin polarization of excitations, the ability to manipulate it optically in external fields, and the possibility to implement quantum correlations between spins, i.e., entanglement. Here it is demonstrated that these conditions are met in bulk crystals of lead halide perovskites. A giant optical orientation of 85% of excitons, approaching the ultimate limit of unity, in FA0.9Cs0.1PbI2.8Br0.2 crystals is reported. The exciton spin orientation is maintained during the exciton lifetime of 55ps resulting in high circular polarization of the exciton emission. The optical orientation is robust to detuning of the excitation energy up to 0.3eV above the exciton resonance and remains larger than 20% up to detunings of 0.9eV. It evidences pure chiral selection rules and suppressed spin relaxation of electrons and holes, even with large kinetic energies. The exciton and electron-hole recombinations are distinguished by means of the spin dynamics detected via coherent spin quantum beats in magnetic field. Further, electron-hole spin correlations are demonstrated through linear polarization beats after circularly polarized excitation. These findings are supported by atomistic calculations. All-in-all, the results establish lead halide perovskite semiconductors as suitable platform for quantumtechnologies.

Electric Field Effects in Hybrid Perovskites Studied via Picosecond Kerr Microscopy.

We present time-resolved Kerr rotation (TRKR) spectra in thin films of CH3NH3PbI3 (MAPI) hybrid perovskite using a unique picosecond microscopy technique at 4 K having a spatial resolution of 2 μm and temporal resolution of 1 ps, subjected to both an in-plane applied magnetic field up to 700 mT and an electric field up to 104 V/cm. We demonstrate that the obtained TRKR dynamics and spectra are substantially inhomogeneous across the MAPI films with prominent resonances at the exciton energy and interband transition of this compound. From the obtained quantum beating response as a function of magnetic field in the Voigt configuration, we also extract the inhomogeneity of the electron and hole Lande g-values and spin coherence time, T2*. We also report the TRKR dependence on both the applied magnetic field and electric field. From the change in the quantum beating dynamics, we found that T2* substantially decreases upon the application of an electric field. At the same time, from the induced spatial TRKR changes, we show that the electric field induced effects are caused by ion migration in the MAPI films.

Nonadiabatic Coupling-Induced Quantum Coherence in Two-Dimensional Materials.

Two-dimensional materials provide a rich platform demonstrating quantum effects, and the process of electron-hole recombination occurring in them has significant applications in the fields of the photocatalytic and optoelectronic community. Here, we present nonadiabatic coupling-induced quantum coherence and quantum beats in Al-doped blue phosphorene. The work improves our understanding and utilization of nonadiabatic coupling in low-dimensional materials from a new perspective. In addition, our investigations provide meaningful guidance for manipulating quantum coherence in low-dimensional materials and promoting their novel optoelectronic properties.

Continuous-Time Quantum Walk in Glued Trees: Localized State-Mediated Almost Perfect Quantum-State Transfer.

In this work, the dynamics of a quantum walker on glued trees is revisited to understand the influence of the architecture of the graph on the efficiency of the transfer between the two roots. Instead of considering regular binary trees, we focus our attention on leafier structures where each parent node could give rise to a larger number of children. Through extensive numerical simulations, we uncover a significant dependence of the transfer on the underlying graph architecture, particularly influenced by the branching rate (M) relative to the root degree (N). Our study reveals that the behavior of the walker is isomorphic to that of a particle moving on a finite-size chain. This chain exhibits defects that originate in the specific nature of both the roots and the leaves. Therefore, the energy spectrum of the chain showcases rich features, which lead to diverse regimes for the quantum-state transfer. Notably, the formation of quasi-degenerate localized states due to significant disparities between M and N triggers a localization process on the roots. Through analytical development, we demonstrate that these states play a crucial role in facilitating almost perfect quantum beats between the roots, thereby enhancing the transfer efficiency. Our findings offer valuable insights into the mechanisms governing quantum-state transfer on trees, with potential applications for the transfer of quantum information.

Asymmetric Tilt-Induced Quantum Beating of Conductance Oscillation in Magnetically Modulated Dirac Matter Systems.

Herein, we investigate the effect of tilt mismatch on the quantum oscillations of spin transport properties in two-dimensional asymmetrically tilted Dirac cone systems. This study involves the examination of conductance oscillation in two distinct junction types: transverse- and longitudinal-tilted Dirac cones (TTDCs and LTDCs). Our findings reveal an unusual quantum oscillation of spin-polarized conductance within the TTDC system, characterized by two distinct anomaly patterns within a single period, labeled as the linear conductance phase and the oscillatory conductance phase. Interestingly, these phases emerge in association with tilt-induced orbital pseudo-magnetization and exchange interaction. Our study also demonstrates that the structure of the LTDC can modify the frequency of spin conductance oscillation, and the asymmetric effect within this structure results in a quantum beating pattern in oscillatory spin conductance. We note that an enhancement in the asymmetric longitudinal tilt velocity ratio within the structure correspondingly amplifies the beating frequency. Our research potentially contributes valuable insights for detecting the asymmetry of tilted Dirac fermions in type-I Dirac semimetal-based spintronics and quantum devices.

Theoretical model of femtosecond coherence spectroscopy of vibronic excitons in molecular aggregates.

When used as pump pulses in transient absorption spectroscopy measurements, femtosecond laser pulses can produce oscillatory signals known as quantum beats. The quantum beats arise from coherent superpositions of the states of the sample and are best studied in the Fourier domain using Femtosecond Coherence Spectroscopy (FCS), which consists of one-dimensional amplitude and phase plots of a specified oscillation frequency as a function of the detection frequency. Prior works have shown ubiquitous amplitude nodes and π phase shifts in FCS from excited-state vibrational wavepackets in monomer samples. However, the FCS arising from vibronic-exciton states in molecular aggregates have not been studied theoretically. Here, we use a model of vibronic-exciton states in molecular dimers based on displaced harmonic oscillators to simulate FCS for dimers in two important cases. Simulations reveal distinct spectral signatures of excited-state vibronic-exciton coherences in molecular dimers that may be used to distinguish them from monomer vibrational coherences. A salient result is that, for certain relative orientations of the transition dipoles, the key resonance condition between the electronic coupling and the frequency of the vibrational mode may yield strong enhancement of the quantum-beat amplitude and, perhaps, also cause a significant decrease of the oscillation frequency to a value far lower than the vibrational frequency. Future studies using these results will lead to new insights into the excited-state coherences generated in photosynthetic pigment-protein complexes.

Quantum Beats between Spin-Singlet and Spin-Triplet Interlayer Exciton Transitions in WSe2-MoSe2 Heterobilayers.

The long-lived interlayer excitons (IXs) of semiconducting transition metal dichalcogenide heterobilayers are prime candidates for developing various optoelectronic and valleytronic devices. Their photophysical properties, including fine structure, have been the focus of recent studies, and the presence of two spin states, namely, spin-singlet and spin-triplet, has been experimentally confirmed. However, the existence of the interaction between these states and their nature remains unknown to date. Here, we demonstrate the presence of coherent coupling between the spin-singlet and spin-triplet IXs of a WSe2-MoSe2 heterobilayer utilizing quantum beat spectroscopy via a home-built Michelson interferometer. As a clear signature of coherent coupling, the quantum beat signal has been observed for the first time between closely spaced transitions of IXs. The observed strong damping of the quantum beat signals with fast dephasing times of 270-400 fs indicates that fluctuations giving rise to inhomogeneous broadening in the photoluminescence emission of these states are uncorrelated.

Spatiotemporal dispersion compensation for a 200-THz noncollinear optical parametric amplifier.

A noncollinear optical parametric amplifier (NOPA) can produce few-cycle femtosecond laser pulses that are ideally suited for time-resolved optical spectroscopy measurements. However, the nonlinear-optical process giving rise to ultrabroadband pulses is susceptible to spatiotemporal dispersion problems. Here, we detail refinements, including chirped-pulse amplification (CPA) and pulse-front matching (PFM), that minimize spatiotemporal dispersion and thereby improve the properties of ultrabroadband pulses produced by a NOPA. The description includes a rationale behind the choices of optical and optomechanical components, as well as assessment protocols. We demonstrate these techniques using a 1kHz, second-harmonic Ti:sapphire pump configuration, which produces ∼5-fs duration pulses that span from about 500 to 800nm with a bandwidth of about 200THz. To demonstrate the utility of the CPA-PFM-NOPA, we measure vibrational quantum beats in the transient-absorption spectrum of methylene blue, a dye molecule that serves as a reference standard.

Ultrafast X-ray Diffraction Probe of Coherent Spin-State Dynamics in Molecules.

We propose an approach to probe coherent spin-state dynamics of molecules using circularly polarized hard X-ray pulses. For the dynamically aligned nitric oxide molecules in a coherent superposition spin-orbit coupled electronic state that can be prepared through stimulated Raman scattering, we demonstrate the capability of ultrafast X-ray diffraction to not only reveal the quantum beating of the coherent spin-state wave packet but also image the spatial spin density of the molecule. With a circularly polarized ultrafast X-ray diffraction signal, we show that the electronic density matrix can be retrieved. The spatiotemporal resolving power of ultrafast X-ray diffraction paves the way for tracking transient spatial wave function in molecular dynamics involving the spin degree of freedom.

Room-temperature quantum coherence of entangled multiexcitons in a metal-organic framework.

Singlet fission can generate an exchange-coupled quintet triplet pair state 5TT, which could lead to the realization of quantum computing and quantum sensing using entangled multiple qubits even at room temperature. However, the observation of the quantum coherence of 5TT has been limited to cryogenic temperatures, and the fundamental question is what kind of material design will enable its room-temperature quantum coherence. Here, we show that the quantum coherence of singlet fission-derived 5TT in a chromophore-integrated metal-organic framework can be over hundred nanoseconds at room temperature. The suppressed motion of the chromophores in ordered domains within the metal-organic framework leads to the enough fluctuation of the exchange interaction necessary for 5TT generation but, at the same time, does not cause severe 5TT decoherence. Furthermore, the phase and amplitude of quantum beating depend on the molecular motion, opening the way to room-temperature molecular quantum computing based on multiple quantum gate control.