A nonadiabatic-transition system which exhibits ``quantum chaotic'' behavior [Phys. Rev. E {\bf 63}, 066221 (2001)] is investigated from quasi-classical aspects. Since such a system does not have a naive classical limit, we take the mapping approach by Stock and Thoss [Phys. Rev. Lett. {\bf 78}, 578 (1997)] to represent the quasi-classical dynamics of the system. We numerically show that there is a sound correspondence between the quantum chaos and classical chaos for the system.
We present a semiclassical quantization condition, i.e., quantum-classical correspondence, for steady states of nonadiabatic systems consisting of fast and slow degrees of freedom (DOFs) by extending Gutzwiller's trace formula to a nonadiabatic form. The quantum-classical correspondence indicates that a set of primitive hopping periodic orbits, which are invariant under time evolution in the phase space of the slow DOF, should be quantized. The semiclassical quantization is then applied to a simple nonadiabatic model and accurately reproduces exact quantum energy levels. In addition to the sem…
This work identifies geometric effects on dynamics due to nonadiabatic couplings in Born Oppenheimer systems and provides a systematic method for deriving corrections to mixed quantum-classical methods. Specifically, an exact path integral formulation of the quantum nonadiabatic dynamics of Born Oppenheimer systems is described. Stationary phase approximations to the propagator for full quantum dynamics are derived. It is shown that quantum corrections to mixed quantum classical methods can be obtained through stationary phase approximations to the full quantum dynamics. A rigorous description…
Quasi-classical Trajectory Calculations on a Two-state Potential Energy Surface Including Nonadiabatic Coupling Terms as Friction for D+ + H2 Collisions
The Born-Oppenheimer (BO) approximation has shaped our understanding on molecular dynamics microscopically in many physical and chemical systems. However, there are many cases that we must go beyond the BO approximation, particularly when strong light-matter interactions are considered. Floquet theory offers a powerful tool to treat time-periodic quantum systems. In this overview, we briefly review recent developments on Floquet nonadiabatic dynamics, with a special focus on open quantum systems. We first present the general Floquet Liouville von-Neumann (LvN) equation. We then show how to con…
A new approximate solution to the quantum-classical Liouville equation is derived starting from the formal solution of this equation in forward-backward form. The time evolution of a mixed quantum-classical system described by this equation is obtained in a coherent state basis using the mapping representation, which expresses $N$ quantum degrees of freedom in a 2N-dimensional phase space. The solution yields a simple non-Hamiltonian dynamics in which a set of $N$ coherent state coordinates evolve in forward and backward trajectories while the bath coordinates evolve under the influence of the…
Mixed-quantum-classical molecular dynamics simulation implies an effective measurement on the electronic states owing to continuously tracking the atomic forces.Based on this insight, we propose a quantum trajectory mean-field approach for nonadiabatic molecular dynamics simulations. The new protocol provides a natural interface between the separate quantum and classical treatments, without invoking artificial surface hopping algorithm. Moreover, it also bridges two widely adopted nonadiabatic dynamics methods, the Ehrenfest mean-field theory and the trajectory surface-hopping method. Excellen…
We derive an exact quantum propagator for nonadiabatic dynamics in multi-state systems using the mapping variable representation, where classical-like Cartesian variables are used to represent both continuous nuclear degrees of freedom and discrete electronic states. The resulting expression is a Moyal series that, when suitably approximated, can allow for the use of classical dynamics to efficiently model large systems. We demonstrate that different truncations of the exact propagator lead to existing approximate semiclassical and mixed quantum-classical methods and we derive an associated er…
We analyze a quantum-classical hybrid system of steadily precessing slow classical localized magnetic moments, forming a head-to-head domain wall, embedded into an open quantum system of fast nonequilibrium electrons. The electrons reside within a metallic wire connected to macroscopic reservoirs. The model captures the essence of dynamical noncollinear and noncoplanar magnetic textures in spintronics, while making it possible to obtain the exact time-dependent nonequilibrium density matrix of electronic system and split it into four contributions. The Fermi surface contribution generates diss…
Quantum computation has demonstrated advantages over classical computation for special hard problems, where a set of universal quantum gates is essential. Geometric phases, which have built-in resilience to local noise, have been used to construct quantum gates with excellent performance. However, this advantage has been smeared in previous schemes. Here, we propose a state-independent nonadiabatic geometric quantum-gate scheme that is able to realize a more fully geometric gate than previous approaches, allowing for the cancelation of dynamical phases accumulated by an arbitrary state. Numeri…
We discuss dynamics of approximate adiabatic invariants in several nonlinear models being related to physics of Bose-Einstein condensates (BEC). We show that nonadiabatic dynamics in Feshbach resonance passage, nonlinear Landau-Zener (NLZ) tunnelling, and BEC tunnelling oscillations in a double-well can be considered within a unifying approach based on the theory of separatrix crossings. The separatrix crossing theory was applied previously to some problems of classical mechanics, plasma physics and hydrodynamics, but has not been used in the rapidly growing BEC-related field yet. We derive ex…
The qualitative nature (i.e. integrable vs. chaotic) of the translational dynamics of a three-level atom in an optical lattice is shown to be controllable by varying the relative laser phase of two standing wave lasers. Control is explained in terms of the nonadiabatic transition between optical potentials and the corresponding regular to chaotic transition in mixed classical-quantum dynamics. The results are of interest to both areas of coherent control and quantum chaos.
An approach to the quantum-classical mechanics of phase space dependent operators, which has been proposed recently, is remodeled as a formalism for wave fields. Such wave fields obey a system of coupled non-linear equations that can be written by means of a suitable non-Hamiltonian bracket. As an example, the theory is applied to the relaxation dynamics of the spin-boson model. In the adiabatic limit, a good agreement with calculations performed by the operator approach is obtained. Moreover, the theory proposed in this paper can take nonadiabatic effects into account without resorting to sur…
The quantum-classical Liouville equation offers a rigorous approach to nonadiabatic quantum dynamics based on surface hopping type trajectories. However, in practice the applicability of this approach has been limited to short times owing to unfavorable numerical scaling. In this paper we show that this problem can be alleviated by combining it with a formally exact generalized quantum master equation treatment. This allows dramatic improvements in the efficiency of the approach in nonadiabatic regimes, making it computationally tractable to treat the quantum dynamics of complex systems for lo…
Fewest-switches surface hopping is studied in the context of quantum-classical Liouville dynamics. Both approaches are mixed quantum-classical theories that provide a way to describe and simulate the nonadiabatic quantum dynamics of many-body systems. Starting from a surface-hopping solution of the quantum-classical Liouville equation, it is shown how fewest-switches dynamics can be obtained by dropping terms that are responsible for decoherence and restricting the nuclear momentum changes that accompany electronic transitions to those events that occur between population states. The analysis …
Nonadiabatic holonomic quantum transformations (NHQTs) have attracted wide attention and have been applied in many aspects of quantum computation, whereas related research is usually limited to the field of quantum physics. Here we bring NHQTs into constructing a unidirectional acoustic metamaterial (UDAM) for shaping classical beams. The UDAM is made up of an array of three-waveguide couplers, where the propagation of acoustic waves mimics the evolution of NHQTs. The excellent agreement among analytical predictions, numerical simulations, and experimental measurements confirms the great appli…
An exact analytical solution is derived for the wavefunction of an electron in a one-dimensional moving quantum dot in a nanowire, in the presence of time-dependent spin-orbit coupling. For cyclic evolutions we show that the spin of the electron is rotated by an angle proportional to the area of a closed loop in the parameter space of the time-dependent quantum dot position and the amplitude of a fictitious classical oscillator driven by the time-dependent spin-orbit coupling. By appropriate choice of parameters, we show that arbitrary spin rotations may be performed on the Bloch sphere. Exact…
The variational quantum eigensolver (VQE) is an algorithm to find eigenenergies and eigenstates of systems in quantum chemistry and quantum many-body physics. The VQE is one of the most promising applications of near-term quantum devices to investigate such systems. Here we propose an extension of the VQE to calculate the nonadiabatic couplings of molecules in quantum chemical systems and Berry's phase in quantum many-body systems. Both quantities play an important role to understand the properties of a system beyond the naive adiabatic picture, e.g., nonadiabatic dynamics and topological phas…
We raise the problem of constructing quantum observables that have classical counterparts without quantization. Specifically we seek to define and motivate a solution to the quantum-classical correspondence problem independent from quantization and discuss the general insufficiency of prescriptive quantization, particularly the Weyl quantization. We demonstrate our points by constructing time of arrival operators without quantization and from these recover their classical counterparts.
Quantum-classical correspondence in chaotic systems is a long-standing problem. We describe a method to quantify Bohr's correspondence principle and calculate the size of quantum numbers for which we can expect to observe quantum-classical correspondence near periodic orbits of Floquet systems. Our method shows how the stability of classical periodic orbits affects quantum dynamics. We demonstrate our method by analyzing quantum-classical correspondence in the quantum kicked top (QKT), which exhibits both regular and chaotic behavior. We use our correspondence conditions to identify signatures…
The investigation of quantum-classical correspondence may lead to gain a deeper understanding of the classical limit of quantum theory. We develop a quantum formalism on the basis of a linear-invariant theorem, which gives an exact quantum-classical correspondence for damped oscillatory systems that are perturbed by an arbitrary force. Within our formalism, the quantum trajectory and expectation values of quantum observables are precisely coincide with their classical counterparts in the case where we remove the global quantum constant h from their quantum results. In particular, we illustrate…
We propose to measure nonadiabaticity of molecular quantum dynamics rigorously with the quantum fidelity between the Born-Oppenheimer and fully nonadiabatic dynamics. It is shown that this measure of nonadiabaticity applies in situations where other criteria, such as the energy gap criterion or the extent of population transfer, fail. We further propose to estimate this quantum fidelity efficiently with a generalization of the dephasing representation to multiple surfaces. Two variants of the multiple-surface dephasing representation (MSDR) are introduced, in which the nuclei are propagated ei…
The oracle model of computation is believed to allow a rigorous proof of quantum over classical computational superiority. Since quantum and classical oracles are essentially different, a correspondence principle is commonly implicitly used as a platform for comparison of oracle complexity. Here, we question the grounds on which this correspondence is based. Obviously, results on quantum speed-up depend on the chosen correspondence. So, we introduce the notion of genuine quantum speed-up which can serve as a tool for reliable comparison of quantum vs classical complexity, independently of the …
We present a means of studying rare reactive pathways in open quantum systems using Transition Path Theory and ensembles of quantum jump trajectories. This approach allows for elucidation of reactive paths for dissipative, nonadiabatic dynamics when the system is embedded in a Markovian environment. We detail the dominant pathways and rates of thermally activated processes, as well as the relaxation pathways and photoyields following vertical excitation in a minimal model of a conical intersection. We find that the geometry of the conical intersection affects the electronic character of the tr…
We point out a correspondence between classical and quantum states, by showing that for every classical distribution over phase--space, one can construct a corresponding quantum state, such that in the classical limit of $\hbar\to 0$ the latter converges to the former with respect to all measurable quantities.
Ising spin Hamiltonians are often used to encode a computational problem in their ground states. Quantum Annealing (QA) computing searches for such a state by implementing a slow time-dependent evolution from an easy-to-prepare initial state to a low energy state of a target Ising Hamiltonian of quantum spins, $H_I$. Here, we point to the existence of an analytical solution for such a problem for an arbitrary $H_I$ beyond the adiabatic limit for QA. This solution provides insights into the accuracy of nonadiabatic computations. Our QA protocol in the pseudo-adiabatic regime leads to a monotoni…
We propose to measure the importance of spin-orbit couplings (SOCs) in the nonadiabatic molecular quantum dynamics rigorously with quantum fidelity. To make the criterion practical, quantum fidelity is estimated efficiently with the multiple-surface dephasing representation (MSDR). The MSDR is a semiclassical method that includes nuclear quantum effects through interference of mixed quantum-classical trajectories without the need for the Hessian of potential energy surfaces. Two variants of the MSDR are studied, in which the nuclei are propagated either with the fewest-switches surface hopping…
Using results from the theory of dynamical systems, we derive a general expression for the classical average scattering dwell time, tau_av. Remarkably, tau_av depends only on a ratio of phase space volumes. We further show that, for a wide class of systems, the average classical dwell time is not in correspondence with the energy average of the quantum Wigner time delay.
A procedure to enhance the quantum--classical correspondence even in situations far from the classical limit is proposed. It is based on controlling the quantum transport between classical regions using the capability to synthesize arbitrary motional states in ion traps. Quantum barriers and passages to transport can be created selecting the relevant frequencies. This technique is then applied to stabilize the quantum motion onto classical structures or alter the dynamical tunneling in nonintegrable systems.
We analyze the connections between entanglement dynamics and classical trajectories in a semiclassi-cal regime for two systems: A pair of coupled oscillators and the Jaynes-Cummings model. We find that entanglement production depends on classical invariant tori and such phenomenon is closely related to the power spectra of classical trajectories. Classical power spectrum with a larger number of frequency com-ponents corresponds to larger entanglement. We introduce a frequency entropy to describe the classical frequency distribution, and find that there is good correspondence between the classi…
We revisit a recent proposal to model nonadiabatic problems with a complex-valued Hamiltonian through a phase-space surface hopping (PSSH) algorithm employing a pseudo-diabatic basis. Here, we show that such a pseudo-diabatic PSSH (PD-PSSH) ansatz is consistent with a quantum-classical Liouville equation (QCLE) that can be derived following a preconditioning process, and we demonstrate that a proper PD-PSSH algorithm is able to capture some geometric magnetic effects (whereas the standard FSSH approach cannot). We also find that a preconditioned QCLE can outperform the standard QCLE in certain…
We recycle Cruz et al.'s (Phys. Lett. A 369 (2007) 400) work on the classical and quantum position-dependent mass (PDM) oscillators. To elaborate on the ordering ambiguity, we properly amend some of the results reported in their work and discuss the classical and quantum mechanical correspondence for the PDM harmonic oscillators. We use a point canonical transformation and show that one unique quantum PDM oscillator Hamiltonian (consequently, one unique ordering-ambiguity parametric set j=l=-1/4 and k=-1/2) is obtained. To show that such a parametric set is not just a manifestation of the quan…
We systematically study several classical-quantum correspondence properties of the dissipative modified kicked rotator, a paradigmatic ratchet model. We explore the behavior of the asymptotic currents for finite $\hbar_{\rm eff}$ values in a wide range of the parameter space. We find that the correspondence between the classical currents with thermal noise providing uctuations of size $\hbar_{\rm eff}$ and the quantum ones without it, is very good in general with the exception of specific regions. We systematically consider the spectra of the corresponding classical Perron-Frobenius operators …
The environment -- external or internal degrees of freedom coupled to the system -- can, in effect, monitor some of its observables. As a result, the eigenstates of these observables decohere and behave like classical states: Continuous destruction of superpositions leads to environment-induced superselection (einselection). Here I investigate it in the context of quantum chaos (i. e., quantum dynamics of systems which are classically chaotic).
We study the decoherence process for an open quantum system which is classically chaotic (a quartic double well with harmonic driving coupled to a sea of harmonic oscillators). We analyze the time dependence of the rate of entropy production showing that it has two relevant regimes: For short times it is proportional to the diffusion coefficient (fixed by the system--environment coupling strength). For longer times (but before equilibration) it is fixed by dynamical properties of the system (and is related to the Lyapunov exponent). The nature of the transition time between both regimes is inv…
Square billiards are quantum systems complying with the dynamical quantum-classical correspondence. Hence an initially localized wavefunction launched along a classical periodic orbit evolves along that orbit, the spreading of the quantum amplitude being controlled by the spread of the corresponding classical statistical distribution. We investigate wavepacket dynamics and compute the corresponding de Broglie-Bohm trajectories in the quantum square billiard. We also determine the trajectories and statistical distribution dynamics for the equivalent classical billiard. Individual Bohmian trajec…
We present a method to study rare nonadiabatic dynamics in open quantum systems using transition path sampling and quantum jump trajectories. As with applications of transition path sampling to classical dynamics, the method does not rely on prior knowledge of transition states or reactive pathways, and thus can provide mechanistic insight into ultrafast relaxation processes in addition to their associated rates. In particular, we formulate a quantum path ensemble using the stochastic realizations of an unravelled quantum master equation, which results in trajectories that can be conditioned o…
We consider a quantum Otto refrigerator cycle of a time-dependent harmonic oscillator. We investigate the coefficient of performance at maximum figure of merit for adiabatic and nonadiabatic frequency modulations. We obtain analytical expressions for the optimal performance both in the high-temperature (classical) regime and in the low-temperature (quantum) limit. We moreover analyze the breakdown of the cooling cycle for strongly nonadiabatic driving protocols and derive analytical estimates for the minimal driving time allowed for cooling.
Nonadiabatic molecular dynamics occur in a wide range of chemical reactions and femtochemistry experiments involving electronically excited states. These dynamics are hard to treat numerically as the system's complexity increases and it is thus desirable to have accurate yet affordable methods for their simulation. Here, we introduce a linearized semiclassical method, the generalized discrete truncated Wigner approximation (GDTWA), which is well-established in the context of quantum spin lattice systems, into the arena of chemical nonadiabatic systems. In contrast to traditional continuous map…
We recently derived a spin-mapping approach for treating the nonadiabatic dynamics of a two-level system in a classical environment [J. Chem. Phys. 151, 044119 (2019)] based on the well-known quantum equivalence between a two-level system and a spin-1/2 particle. In the present paper, we generalize this method to describe the dynamics of $N$-level systems. This is done via a mapping to a classical phase space that preserves the $SU(N)$-symmetry of the original quantum problem. The theory reproduces the standard Meyer--Miller--Stock--Thoss Hamiltonian without invoking an extended phase space, a…
While the emergent field of quantum thermodynamics has the potential to impact energy science, the performance of thermal machines is often classical. We ask whether quantum effects can boost the performance of a thermal machine to reach quantum supremacy, i.e., surpassing both the efficiency and power achieved in classical thermodynamics. To this end, we introduce a nonadiabatic quantum heat engine operating an Otto cycle with a many-particle working medium, consisting of an interacting Bose gas confined in a time-dependent harmonic trap. It is shown that thanks to the interplay of nonadiabat…
We set up a general density-operator approach to geometric steady-state pumping through slowly driven open quantum systems. This approach applies to strongly interacting systems that are weakly coupled to multiple reservoirs at high temperature, illustrated by an Anderson quantum dot, but shows potential for generalization. Pumping gives rise to a nonadiabatic geometric phase that can be described by a framework originally developed for classical dissipative systems by Landsberg. This geometric phase is accumulated by the transported observable (charge, spin, energy) and not by the quantum sta…
Quantum-classical correspondence in conservative chaotic Hamiltonian systems is examined using a uniform structure measure for quantal and classical phase space distribution functions. The similarities and differences between quantum and classical time-evolving distribution functions are exposed by both analytical and numerical means. The quantum-classical correspondence of low-order statistical moments is also studied. The results shed considerable light on quantum-classical correspondence.
We prove quantum-classical correspondence for bound conservative classically chaotic Hamiltonian systems. In particular, quantum Liouville spectral projection operators and spectral densities, and hence classical dynamics, are shown to approach their classical analogs in the $h\rightarrow 0$ limit. Correspondence is shown to occur via the elimination of essential singularities. In addition, applications to matrix elements of observables in chaotic systems are discussed.
We consider the problem of quantum-classical correspondence in integrable field theories. We propose a method to construct a field theoretical coherent state, in which the expectation value of the quantum field operator exactly coincides with the classical soliton. We also discuss the time evolution of this quantum state and the instability due to the nonlinearity.
We propose to study the $L^2$-norm distance between classical and quantum phase space distributions, where for the latter we choose the Wigner function, as a global phase space indicator of quantum-classical correspondence. For example, this quantity should provide a key to understand the correspondence between quantum and classical Loschmidt echoes. We concentrate on fully chaotic systems with compact (finite) classical phase space. By means of numerical simulations and heuristic arguments we find that the quantum-classical fidelity stays at one up to Ehrenfest-type time scale, which is propo…
We numerically study the work distributions in a chaotic system and examine the relationship between quantum work and classical work. Our numerical results suggest that there exists a correspondence principle between quantum and classical work distributions in a chaotic system. This correspondence was proved for one-dimensional (1D) integrable systems in a recent work [Jarzynski, Quan, and Rahav, Phys. Rev. X 5, 031038 (2015)]. Our investigation further justifies the definition of quantum work via two point energy measurements.
Correspondence in quantum chaotic systems is lost in short time scales. Introducing some noise we study the spectrum of the resulting coarse grained propagaor of density matrices. Some differen methods to compute the spectrum are reviewed. Moreover, the relationship between the eigenvalues of the coarse-grained superoperator and the classical Ruelle-Pollicott resonances is remarked. As a concequence, classical decay rates in quantum time dependent quantities appear.
Spectra of the geometric collective model of atomic nuclei are analyzed to identify chaotic correlations among nonrotational states. The model has been previously shown to exhibit a high degree of variability of regular and chaotic classical features with energy and control parameters. Corresponding signatures are now verified also on the quantum level for different schemes of quantization and with a variable classicality constant.
We formulate the theory of shortcuts to adiabaticity in classical mechanics. For a reference Hamiltonian, the counterdiabatic term is constructed from the dispersionless Korteweg-de Vries (KdV) hierarchy. Then the adiabatic theorem holds exactly for an arbitrary choice of time-dependent parameters. We use the Hamilton-Jacobi theory to define the generalized action. The action is independent of the history of the parameters and is directly related to the adiabatic invariant. The dispersionless KdV hierarchy is obtained from the classical limit of the KdV hierarchy for the quantum shortcuts to a…
Classical-quantum correspondence for conservative chaotic Hamiltonians is investigated in terms of the structure of the eigenfunctions and the local density of states, using as a model a 2D rippled billiard in the regime of global chaos. The influence of the observed localized and sparsed states in the quantum-classical correspondence is discussed.
