Full Quantum Treatment Research Articles

Resonant Tunnelling and Intersubband Optical Properties of ZnO/ZnMgO Semiconductor Heterostructures: Impact of Doping and Layer Structure Variation.

ZnO-based heterostructures are up-and-coming candidates for terahertz (THz) optoelectronic devices, largely owing to their innate material attributes. The significant ZnO LO-phonon energy plays a pivotal role in mitigating thermally induced LO-phonon scattering, potentially significantly elevating the temperature performance of quantum cascade lasers (QCLs). In this work, we calculate the electronic structure and absorption of ZnO/ZnMgO multiple semiconductor quantum wells (MQWs) and the current density-voltage characteristics of nonpolar m-plane ZnO/ZnMgO double-barrier resonant tunnelling diodes (RTDs). Both MQWs and RTDs are considered here as two building blocks of a QCL. We show how the doping, Mg percentage and layer thickness affect the absorption of MQWs at room temperature. We confirm that in the high doping concentrations regime, a full quantum treatment that includes the depolarisation shift effect must be considered, as it shifts mid-infrared absorption peak energy for several tens of meV. Furthermore, we also focus on the performance of RTDs for various parameter changes and conclude that, to maximise the peak-to-valley ratio (PVR), the optimal doping density of the analysed ZnO/Zn88Mg12O double-barrier RTD should be approximately 1018 cm-3, whilst the optimal barrier thickness should be 1.3 nm, with a Mg mole fraction of ~9%.

Zeno Regime of Collective Emission: Non-Markovianity beyond Retardation.

To build up a collective emission, the atoms in an ensemble must coordinate their behavior by exchanging virtual photons. We study this non-Markovian process in a subwavelength atom chain coupled to a one-dimensional (1D) waveguide and find that retardation is not the only cause of non-Markovianity. The other factor is the memory of the photonic environment, for which a single excited atom needs a finite time, the Zeno regime, to transition from quadratic decay to exponential decay. In the waveguide setup, this crossover has a time scale longer than the retardation, thus impacting the development of collective behavior. By comparing a full quantum treatment with an approach incorporating only the retardation effect, we find that the field memory effect, characterized by the population of atomic excitation, is much more pronounced in collective emissions than that in the decay of a single atom. Our results maybe useful for the dissipation engineering of quantum information processings based on compact atom arrays.

Driven-Dissipative Time Crystalline Phases in a Two-Mode Bosonic System with Kerr Nonlinearity.

For the driven-dissipative system of two coupled bosonic modes in a nonlinear cavity resonator, we demonstrate a sequence of phase transitions from a trivial steady state to two distinct dissipative time crystalline phases. These effects are already anticipated at the level of the semiclassical analysis of the Lindblad equation using the theory of bifurcations and are further supported by the full quantum treatment. The system is predicted to exhibit different dynamical phases characterized by an oscillating nonequilibrium steady state with nontrivial periodicity, which is a hallmark of time crystals. We expect that these phases can be directly probed in various cavity QED experiments.

Resonant tunneling diodes in semiconductor microcavities: Modeling polaritonic features in the terahertz displacement current

We develop in this work a simple qualitative quantum electron transport model, in the strong light-matter coupling regime under dipole approximation, able to capture polaritonic signatures in the time-dependent electrical current. The effect of the quantized electromagnetic field in the displacement current of a resonant tunneling diode inside an optical cavity is analyzed. The original peaks of the bare electron transmission coefficient split into two new peaks due to the resonant electron-photon interaction, leading to coherent Rabi oscillations among the polaritonic states that are developed in the system in the strong coupling regime. This mimics known effects predicted by a Jaynes-Cummings model in closed systems, and shows how a full quantum treatment of electrons and electromagnetic fields may open interesting paths for engineering new THz electron devices. The computational burden involved in the multi-time measurements of THz currents is tackled by invoking a Bohmian description of the light-matter interaction. We also show that the traditional static transmission coefficient used to characterize DC quantum electron devices has to be substituted by a new displacement current coefficient in high-frequency AC scenarios.

Ultrafast Charge Relocation Dynamics in Enol-Keto Tautomerization Monitored with a Local Soft-X-ray Probe.

Proton-coupled electron transfer (PCET) is the underlying mechanism governing important reactions ranging from water splitting in photosynthesis to oxygen reduction in hydrogen fuel cells. The interplay of proton and electronic charge distribution motions can vary from sequential to concerted schemes, with elementary steps occurring on ultrafast time scales. We demonstrate with a simulation study that femtosecond soft-X-ray spectroscopy provides key insights into the PCET mechanism of a photoinduced intramolecular enol* → keto* tautomerization reaction. A full quantum treatment of the electronic and nuclear dynamics of 2-(2′-hydroxyphenyl)benzothiazole upon electronic excitation reveals how spectral signatures of local excitations from core to frontier orbitals display the distinctly different stages of charge relocation for the H atom, donating, and accepting sites. Our findings indicate that ultraviolet/X-ray pump-probe spectroscopy provides a unique way to probe ultrafast electronic structure rearrangements in photoinduced chemical reactions essential to understanding the mechanism of PCET.

Periodic Cavity State Revivals from Atomic Frequency Combs.

Spin ensembles with a comb-shaped spectrum have shown exciting properties as efficient quantum memories. Here, we present a rigorous theoretical study of such atomic frequency combs in the strong coupling limit of cavity QED, based on a full quantum treatment using tensor-network methods. Our results demonstrate that arbitrary multiphoton states in the cavity are almost perfectly absorbed by the spin ensemble and reemitted as parity-flipped states at periodic time intervals. Fidelity values near unity are achieved in these revived states by compensating for energy shifts induced by the strong spin-cavity coupling through adjustments of individual coupling values of the teeth in the atomic frequency comb.

Efficient simulation of ultrafast quantum nonlinear optics with matrix product states

Ultrashort pulses propagating in nonlinear nanophotonic waveguides can simultaneously leverage both temporal and spatial field confinement, promising a route towards single-photon nonlinearities in an all-photonic platform. In this multimode quantum regime, however, faithful numerical simulations of pulse dynamics naïvely require a representation of the state in an exponentially large Hilbert space. Here, we employ a time-domain, matrix product state (MPS) representation to enable efficient simulations by exploiting the entanglement structure of the system. To extract physical insight from these simulations, we develop an algorithm to unravel the MPS quantum state into constituent temporal supermodes, enabling, e.g., access to the phase-space portraits of arbitrary pulse waveforms. As a demonstration, we perform exact numerical simulations of a Kerr soliton in the quantum regime. We observe the development of non-classical Wigner-function negativity in the solitonic mode as well as quantum corrections to the semiclassical dynamics of the pulse. A similar analysis of χ ( 2 ) simultons reveals a unique entanglement structure between the fundamental and second harmonics. Our approach is also readily compatible with quantum trajectory theory, allowing full quantum treatment of propagation loss and decoherence. We expect this work to establish the MPS technique as part of a unified engineering framework for the emerging field of broadband quantum photonics.

Time-dependent variational dynamics for nonadiabatically coupled nuclear and electronic quantum wavepackets in molecules

We propose a methodology to unify electronic and nuclear quantum wavepacket dynamics in molecular processes including nonadiabatic chemical reactions. The canonical and traditional approach in the full quantum treatment both for electrons and nuclei rests on the Born–Oppenheimer fixed nuclei strategy, the total wavefunction of which is described in terms of the Born–Huang expansion. This approach is already realized numerically but only for small molecules with several number of coupled electronic states for extremely hard technical reasons. Besides, the stationary-state view of the relevant electronic states based on the Born–Oppenheimer approximation is not always realistic in tracking real-time electron dynamics in attosecond scale. We therefore incorporate nuclear wavepacket dynamics into the scheme of nonadiabatic electron wavepacket theory, which we have been studying for a long time. In this scheme thus far, electron wavepackets are quantum mechanically propagated in time along nuclear paths that can naturally bifurcate due to nonadiabatic interactions. The nuclear paths are in turn generated simultaneously by the so-called matrix force given by the electronic states involved, the off-diagonal elements of which represent the force arising from nonadiabatic interactions. Here we advance so that the nuclear wavepackets are directly taken into account in place of path (trajectory) approximation. The nuclear wavefunctions are represented in terms of the Cartesian Gaussians multiplied by plane waves, which allows for feasible calculations of atomic and molecular integrals together with the electronic counterparts in a unified manner. The Schrödinger dynamics of the simultaneous electronic and nuclear wavepackets are to be integrated by means of the dual least action principle of quantum mechanics [K. Takatsuka, J. Phys. Commun. 4, 035007 (2020)], which is a time-dependent variational principle. Great contributions of Vincent McKoy in the electron dynamics in the fixed nuclei approximation and development in time-resolved photoelectron spectroscopy are briefly outlined as a guide to the present work.

Effects of spin-phonon coupling in frustrated Heisenberg models

The existence and stability of spin-liquid phases represent a central topic in the field of frustrated magnetism. While a few examples of spin-liquid ground states are well established in specific models (e.g. the Kitaev model on the honeycomb lattice), recent investigations have suggested the possibility of their appearance in several Heisenberg-like models on frustrated lattices. An important related question concerns the stability of spin liquids in the presence of small perturbations in the Hamiltonian. In this respect, the magnetoelastic interaction between spins and phonons represents a relevant and physically motivated perturbation, which has been scarcely investigated so far. In this work, we study the effect of the spin-phonon coupling on prototypical models of frustrated magnetism. We adopt a variational framework based upon Gutzwiller-projected wave functions implemented with a spin-phonon Jastrow factor, providing a full quantum treatment of both spin and phonon degrees of freedom. The results on the frustrated $J_1-J_2$ Heisenberg model on one- and two-dimensional (square) lattices show that, while a valence-bond crystal is prone to lattice distortions, a gapless spin liquid is stable for small spin-phonon couplings. In view of the ubiquitous presence of lattice vibrations, our results are particularly important to demonstrate the possibility that gapless spin liquids may be realized in real materials.

Generalized electromagnetic theorems for nonlocal plasmonics

The ultraconfined light of plasmonic modes put their effective wavelength close to the mean free path of electrons inside the metal electron gas. The Drude model, which can not take the repulsive interactions of electrons into account, then clearly begins to show its limits. In an intermediate length scale where a full quantum treatment is computationally prohibitive, the semiclassical hydrodynamic model, instrinsically non-local, has proven successful. Here we generalize the expression for the absorption volume density and the reciprocity theorem in the framework of this hydrodynamic model. We validate numerically these generalized theorems and show that using classical expressions instead leads to large discrepancies.

Vibrational State-to-State Scattering of Water from Cu(111): Comparison of Quantum and Quasiclassical Methods with Normal Mode and Adiabatic Switching Sampling

Vibrational energy transfer of a polyatomic molecule upon collision at a solid surface is of fundamental importance in surface chemistry. As a full quantum treatment of this process is extremely ch...

Kinetic envelope soliton in non-thermal quantum pair-ion plasma and Wigner stability

Using Wigner–Moyal formulation for the pair-ion plasma, with the residual electrons present we have derived the nonlinear Schrödinger equation for the kinetic envelope soliton with the help of Krylov–Bogoliubov–Mitropolsky approach. This is a full-quantum mechanical treatment of the problem where all the species (both ion and electrons) are treated on the same footing. The stability property of the nonlinear Schrödinger equation is then analyzed with the help of Wigner-transform in phase space. Our approach has the advantage that one can study the stability for various form of initial spectral distribution. The standard modulational stability is a special case of this approach. The experimental observation of the temperature difference between the species in pair ion is taken care of by the Cairns non-thermal distribution. It is observed that non-thermality has a good influence on the propagation characteristics and on the stability properties.

Hybrid-Liouvillian formalism connecting exceptional points of non-Hermitian Hamiltonians and Liouvillians via postselection of quantum trajectories

Exceptional points (EPs) are degeneracies of classical and quantum open systems, which are studied in many areas of physics including optics, optoelectronics, plasmonics, and condensed matter physics. In the semiclassical regime, open systems can be described by phenomenological effective non-Hermitian Hamiltonians (NHHs) capturing the effects of gain and loss in terms of imaginary fields. The EPs that characterize the spectra of such Hamiltonians (HEPs) describe the time evolution of a system without quantum jumps. It is well known that a full quantum treatment describing more generic dynamics must crucially take into account such quantum jumps. In a recent paper [F. Minganti $et$ $al.$, Phys. Rev. A $\mathbf{100}$, $062131$ ($2019$)], we generalized the notion of EPs to the spectra of Liouvillian superoperators governing open system dynamics described by Lindblad master equations. Intriguingly, we found that in situations where a classical-to-quantum correspondence exists, the two types of dynamics can yield different EPs. In a recent experimental work [M. Naghiloo $et$ $al.$, Nat. Phys. $\mathbf{15}$, $1232$ ($2019$)], it was shown that one can engineer a non-Hermitian Hamiltonian in the quantum limit by postselecting on certain quantum jump trajectories. This raises an interesting question concerning the relation between Hamiltonian and Lindbladian EPs, and quantum trajectories. We discuss these connections by introducing a hybrid-Liouvillian superoperator, capable of describing the passage from an NHH (when one postselects only those trajectories without quantum jumps) to a true Liouvillian including quantum jumps (without postselection). Beyond its fundamental interest, our approach allows to intuitively relate the effects of postselection and finite-efficiency detectors.

From Molecular Aggregation to a One-Dimensional Quantum Crystal of Deuterium Inside a Carbon Nanotube of 1 nm Diameter.

The quantum motion of clusters of up to four deuterium molecules under confinement in a single-wall (1 nm diameter) carbon nanotube is investigated by applying a highly accurate full quantum treatment of the most relevant nuclear degrees of freedom and an ab initio-derived potential model of the underlying dispersion-dominated intermolecular interactions. The wave functions and energies are calculated using an ad hoc-developed discrete variable representation (DVR) numerical approach in internal coordinates, with the space grid approaching a few billion grid points. We unambiguously demonstrate the formation of a solid-like pyramidal one-dimensional chain structure of molecules under the cylindrical nanotube confinement. The onset of solid-like packing is explained by analyzing the potential minima landscape. The stabilization of collective rotational motion through "rigid rotations" of four deuterium molecules provides conclusive evidence for the onset of a quantum solid-like behavior resembling that of quantum rings featuring persistent current (charged particles) or persistent flow (neutral particles).

Analytic solutions for the spatial character and coherence properties of light scattered from two dipole-coupled atoms

Analytic solutions for steady-state expectation values of atomic quantities and second order correlations are obtained for a fully quantum treatment of two stationary dipole-coupled atoms driven in a standard geometric configuration by a near resonant laser. Explicit expressions for the spatial and coherence properties of the far-field scattered light intensity are derived, valid for the full range of system parameters. A comprehensive survey of the steady-state scattering behaviour is given, with key features precisely characterised, including subradiant scattering, and the regime in which the dipole-dipole coupling has significant effect. A regime is also found where the incoherent scattered light develops spatial interference fringes. We examine in detail a decorrelation approximation that has potential application for larger systems of atoms that are intractable in a full quantum treatment. Finally, we introduce the concept of an effective driving field and show that it can provide a direct and intuitive physical interpretation of key aspects of the system behaviour, including subradiant scattering.

On the expected production of gravitational waves during preheating

The existing predictions of the energy density of gravitational waves produced during preheating mostly rely on computer simulations in which the matter field inhomogeneities essentially behave classically. In this article we follow instead a full quantum treatment of the process within the in-in formalism. We use this approach to determine the expected density of the produced gravitational waves and numerically estimate its value in a simple scalar field model, neglecting backreaction. Particular attention is devoted to the regularization and renormalization of the divergences that appear in the in-in formalism. We also address how our approach compares with the conventional calculations used in the literature, and what elements could be missed in the conventional analyses of gravitational wave production that rely on numerical simulations. In the cases in which parametric resonance is effective, our results agree with the predictions expected from numerical simulations, as anticipated. At sufficiently low values of the resonance parameter, however, numerical simulations fail, while our approach remains applicable.

Quantum effects in muon spin spectroscopy within the stochastic self-consistent harmonic approximation

In muon spin rotation experiments the positive implanted muon vibrates with large zero point amplitude by virtue of its light mass. Quantum mechanical calculations of the host material usually treat the muon as a point impurity, ignoring this large vibrational amplitude. As a first order correction, the muon zero point motion is usually described within the harmonic approximation, despite the large anharmonicity of the crystal potential. Here we apply the stochastic self-consistent harmonic approximation, a quantum variational method devised to include strong anharmonic effects in total energy and vibrational frequency calculations, in order to overcome these limitations and provide an accurate ab initio description of the quantum nature of the muon. We applied this full quantum treatment to the calculation of the muon contact hyperfine field in textbook-case metallic systems, such as Fe, Ni, Co including MnSi and MnGe, significantly improving agreement with experiments. Our results show that muon vibrational frequencies are strongly renormalized by anharmonicity. Finally, in contrast to the harmonic approximation, we show that including quantum anharmonic fluctuations, the muon stabilizes at the octahedral site in bcc Fe.

Evidence of Extreme Ultraviolet Superfluorescence in Xenon

We present a comprehensive experimental and theoretical study on superfluorescence in the extreme ultraviolet wavelength regime. Focusing a free-electron laser pulse in a cell filled with Xe gas, the medium is quasi-instantaneously population inverted by 4d-shell ionization on the giant resonance followed by Auger decay. On the timescale of ∼10 ps to ∼100 ps (depending on parameters) a macroscopic polarization builds up in the medium, resulting in superfluorescent emission of several Xe lines in the forward direction. As the number of emitters in the system is increased by either raising the pressure or the pump-pulse energy, the emission yield grows exponentially over four orders of magnitude and reaches saturation. With increasing yield, we observe line broadening, a manifestation of superfluorescence in the spectral domain. Our novel theoretical approach, based on a full quantum treatment of the atomic system and the irradiated field, shows quantitative agreement with the experiment and supports our interpretation.

Modeling the Structural and Thermal Properties of Loaded Metal–Organic Frameworks. An Interplay of Quantum and Anharmonic Fluctuations

Metal-organic frameworks show both fundamental interest and great promise for applications in adsorption-based technologies, such as the separation and storage of gases. The flexibility and complexity of the molecular scaffold pose a considerable challenge to atomistic modeling, especially when also considering the presence of guest molecules. We investigate the role played by quantum and anharmonic fluctuations in the archetypical case of MOF-5, comparing the material at various levels of methane loading. Accurate path integral simulations of such effects are made affordable by the introduction of an accelerated simulation scheme and the use of an optimized force field based on first-principles reference calculations. We find that the level of statistical treatment that is required for predictive modeling depends significantly on the property of interest. The thermal properties of the lattice are generally well described by a quantum harmonic treatment, with the adsorbate behaving in a classical but strongly anharmonic manner. The heat capacity of the loaded framework-which plays an important role in the characterization of the framework and in determining its stability to thermal fluctuations during adsorption/desorption cycles-requires, however, a full quantum and anharmonic treatment, either by path integral methods or by a simple but approximate scheme. We also present molecular-level insight into the nanoscopic interactions contributing to the material's properties and suggest design principles to optimize them.

Density-Matrix Embedding Theory Study of the One-Dimensional Hubbard-Holstein Model.

We present a density-matrix embedding theory (DMET) study of the one-dimensional Hubbard–Holstein model, which is paradigmatic for the interplay of electron–electron and electron–phonon interactions. Analyzing the single-particle excitation gap, we find a direct Peierls insulator to Mott insulator phase transition in the adiabatic regime of slow phonons in contrast to a rather large intervening metallic phase in the anti-adiabatic regime of fast phonons. We benchmark the DMET results for both on-site energies and excitation gaps against density-matrix renormalization group (DMRG) results and find good agreement of the resulting phase boundaries. We also compare the full quantum treatment of phonons against the standard Born–Oppenheimer (BO) approximation. The BO approximation gives qualitatively similar results to DMET in the adiabatic regime but fails entirely in the anti-adiabatic regime, where BO predicts a sharp direct transition from Mott to Peierls insulator, whereas DMET correctly shows a large intervening metallic phase. This highlights the importance of quantum fluctuations in the phononic degrees of freedom for metallicity in the one-dimensional Hubbard–Holstein model.