Real-time Quantum Dynamics Research Articles

Real-time quantum dynamics of thermal states with neural thermofields

Real-time quantum dynamics of thermal states with neural thermofields

Simple and General Unitarity Conserving Numerical Real-Time Propagators of the Time-Dependent Schrödinger Equation Based on Magnus Expansion.

Magnus expansion (ME) provides a general way to expand the real-time propagator of a time-dependent Hamiltonian within the exponential such that the unitarity is satisfied at any order. We use this property and explicit integration of Lagrange interpolation formulas for the time-dependent Hamiltonian within each time interval and derive approximations that preserve unitarity for the differential time evolution operators of general time-dependent Hamiltonians. The resulting second-order approximation is the same as using the average of Hamiltonians for two end points of time. We identify three fourth-order approximations involving commutators of Hamiltonians at different times and also derive a sixth-order expression. A test of these approximations along with other available expressions for a two-state time-dependent Hamiltonian with sinusoidal time dependences provides information on the relative performance of these approximations and suggests that the derived expressions can serve as useful numerical tools for time evolution in time-resolved spectroscopy, quantum control, quantum sensing, real-time ab initio quantum dynamics, and open system quantum dynamics.

Holstein polaron transport from numerically "exact" real-time quantum dynamics simulations.

Numerically "exact" methods addressing the dynamics of coupled electron-phonon systems have been intensively developed. Nevertheless, the corresponding results for the electron mobility μdc are scarce, even for the one-dimensional (1d) Holstein model. Building on our recent progress on single-particle properties, here we develop the momentum-space hierarchical equations of motion (HEOM) method to evaluate real-time two-particle correlation functions of the 1d Holstein model at a finite temperature. We compute numerically "exact" dynamics of the current-current correlation function up to real times sufficiently long to capture the electron's diffusive motion and provide reliable results for μdc in a wide range of model parameters. In contrast to the smooth ballistic-to-diffusive crossover in the weak-coupling regime, we observe a temporally limited slow-down of the electron on intermediate time scales already in the intermediate-coupling regime, which translates to a finite-frequency peak in the optical response. Our momentum-space formulation lowers the numerical effort with respect to existing HEOM-method implementations, while we remove the numerical instabilities inherent to the undamped-mode HEOM by devising an appropriate hierarchy closing scheme. Still, our HEOM remains unstable at too low temperatures, for too strong electron-phonon coupling, and for too fast phonons.

Ab initio real-time quantum dynamics of charge carriers in momentum space.

Application of the non-adiabatic molecular dynamics (NAMD) approach is limited to studying carrier dynamics in the momentum space, as a supercell is required to sample the phonon excitation and electron-phonon (e-ph) interaction at different momenta in a molecular dynamics simulation. Here we develop an ab initio approach for the real-time charge carrier quantum dynamics in the momentum space (NAMD_k) by directly introducing e-ph coupling into the Hamiltonian based on the harmonic approximation. The NAMD_k approach maintains the zero-point energy and includes memory effects of carrier dynamics. The application of NAMD_k to the hot carrier dynamics in graphene reveals the phonon-specific relaxation mechanism. An energy threshold of 0.2 eV-defined by two optical phonon modes-separates the hot electron relaxation into fast and slow regions with lifetimes of pico- and nanoseconds, respectively. The NAMD_k approach provides an effective tool to understand real-time carrier dynamics in the momentum space for different materials.

Electronic Born-Oppenheimer approximation in nuclear-electronic orbital dynamics.

Within the nuclear-electronic orbital (NEO) framework, the real-time NEO time-dependent density functional theory (RT-NEO-TDDFT) approach enables the simulation of coupled electronic-nuclear dynamics. In this approach, the electrons and quantum nuclei are propagated in time on the same footing. A relatively small time step is required to propagate the much faster electronic dynamics, thereby prohibiting the simulation of long-time nuclear quantum dynamics. Herein, the electronic Born-Oppenheimer (BO) approximation within the NEO framework is presented. In this approach, the electronic density is quenched to the ground state at each time step, and the real-time nuclear quantum dynamics is propagated on an instantaneous electronic ground state defined by both the classical nuclear geometry and the nonequilibrium quantum nuclear density. Because the electronic dynamics is no longer propagated, this approximation enables the use of an order-of-magnitude larger time step, thus greatly reducing the computational cost. Moreover, invoking the electronic BO approximation also fixes the unphysical asymmetric Rabi splitting observed in previous semiclassical RT-NEO-TDDFT simulations of vibrational polaritons even for small Rabi splitting, instead yielding a stable, symmetric Rabi splitting. For the intramolecular proton transfer in malonaldehyde, both RT-NEO-Ehrenfest dynamics and its BO counterpart can describe proton delocalization during the real-time nuclear quantum dynamics. Thus, the BO RT-NEO approach provides the foundation for a wide range of chemical and biological applications.

Convergence condition of simulated quantum annealing for closed and open systems

Simulated quantum annealing is a generic classical protocol to simulate some aspects of quantum annealing and is sometimes regarded as a classical alternative to quantum annealing in finding the ground state of a classical Ising model. We derive a generic condition for simulated quantum annealing to converge to thermal equilibrium at a given, typically low, temperature. Both closed and open systems are treated. We rewrite the classical master equation for simulated quantum annealing into an imaginary-time Schr\"odinger equation, to which we apply the imaginary-time variant of asymptotic adiabatic condition to deduce the convergence condition. The result agrees qualitatively with a rigorous convergence condition of simulated quantum annealing for closed systems, which was derived from the theory of inhomogeneous Markov process. Also observed is qualitative agreement with a rigorous convergence condition of quantum annealing for closed systems under the real-time Schr\"odinger dynamics. This coincidence of convergence conditions for classical stochastic processes for simulated quantum annealing and the real-time quantum dynamics for quantum annealing is highly non-trivial and calls for further scrutiny.

Random Quantum Circuits

Quantum circuits—built from local unitary gates and local measurements—are a new playground for quantum many-body physics and a tractable setting to explore universal collective phenomena far from equilibrium. These models have shed light on longstanding questions about thermalization and chaos, and on the underlying universal dynamics of quantum information and entanglement. In addition, such models generate new sets of questions and give rise to phenomena with no traditional analog, such as dynamical phase transitions in quantum systems that are monitored by an external observer. Quantum circuit dynamics is also topical in view of experimental progress in building digital quantum simulators that allow control of precisely these ingredients. Randomness in the circuit elements allows a high level of theoretical control, with a key theme being mappings between real-time quantum dynamics and effective classical lattice models or dynamical processes. Many of the universal phenomena that can be identified in this tractable setting apply to much wider classes of more structured many-body dynamics.

Plasmon-induced excitation energy transfer in silver nanoparticle dimers: A real-time TDDFTB investigation.

Using real-time quantum dynamics calculations, we perform theoretical investigations of light-induced interactions and electronic excitation transfer in a silver nanoparticle dimer. Real-time time-dependent density functional tight-binding (RT-TDDFTB) calculations provide details of the quantum dynamical processes at an electronic/atomistic level with attosecond resolution. The computational efficiency of RT-TDDFTB allows us to examine electronic dynamics up to picosecond time scales. With time scales varying over six orders of magnitude, we provide insight into interactions between the nanoparticle and laser and between nanoparticles. Our results show that the coupling between nanoparticle monomers is dependent on the separation distance between the nanoparticles in the dimer. As the interparticle distance is varied, the dipole-dipole interactions and electronic excitation transfer mechanisms are markedly different. At large distances (from 50 to 20 Å), the energy transfer from NP1 to NP2 becomes more efficient as the interparticle distance decreases. The total dipole moment of the Ag14 nanoparticle dimer increases linearly at an interparticle distance of 20 Å and reaches its maximum after 1.2ps. The electronic excitation transfer is also the most efficient at 20 Å. At short distances, back-transfer effects reduce the ability of the dimer and NP1 to accept energy from the incident electric field. We attribute the distance-dependent features of the nanoparticle dimer to the beating between the laser acting on NP1 and the back transfer from NP2 to NP1.

Bounding the finite-size error of quantum many-body dynamics simulations

Finite-size error (FSE), the discrepancy between an observable in a finite system and in the thermodynamic limit, is ubiquitous in numerical simulations of quantum many body systems. Although a rough estimate of these errors can be obtained from a sequence of finite-size results, a strict, quantitative bound on the magnitude of FSE is still missing. Here we derive rigorous upper bounds on the FSE of local observables in real time quantum dynamics simulations initialized from a product state. In $d$-dimensional locally interacting systems with a finite local Hilbert space, our bound implies $ |\langle \hat{S}(t)\rangle_L-\langle \hat{S}(t)\rangle_\infty|\leq C(2v t/L)^{cL-\mu}$, with $v$, $C$, $c$, $\mu $ constants independent of $L$ and $t$, which we compute explicitly. For periodic boundary conditions (PBC), the constant $c$ is twice as large as that for open boundary conditions (OBC), suggesting that PBC have smaller FSE than OBC at early times. The bound can be generalized to a large class of correlated initial states as well. As a byproduct, we prove that the FSE of local observables in ground state simulations decays exponentially with $L$, under a suitable spectral gap condition. Our bounds are practically useful in determining the validity of finite-size results, as we demonstrate in simulations of the one-dimensional (1D) quantum Ising and Fermi-Hubbard models.

Theoretical Analysis of the Formylmethylene Anion Photoelectron Spectrum: Importance of Wolff Rearrangement Dynamics.

Photoelectron spectroscopy of a molecular anion is very useful for investigating the transition state and intermediate regions on the reactive potential energy surfaces of a neutral system. In this work, we theoretically analyzed the previously measured photoelectron spectrum of the formylmethylene anion, HCCHO-. We simulated the photoelectron spectra for both the singlet and triplet states using the semiclassical method with quantum nuclear densities and Franck-Condon factor calculations with harmonic vibrational analysis. We also performed real-time quantum dynamics calculations to elucidate the importance of the Wolff rearrangement process, which leads to the stable product ketene from the carbene intermediate on the neutral singlet potential energy surface.

Real-time quantum dynamics, path integrals and the method of thimbles

Direct numerical evaluation of the real-time path integral has a well-known sign problem that makes convergence exponentially slow. One promising remedy is to use Picard-Lefschetz theory to flow the domain of the field variables into the complex plane, where the integral is better behaved. By Cauchy’s theorem, the final value of the path integral is unchanged. Previous analyses have considered the case of real scalar fields in thermal equilibrium, employing a closed Schwinger-Keldysh time contour, allowing the evaluation of the full quantum correlation functions. Here we extend the analysis by not requiring a closed time path, instead allowing for an initial density matrix for out-of-equilibrium initial value problems. We are able to explicitly implement Gaussian initial conditions, and by separating the initial time and the later times into a two-step Monte-Carlo sampling, we are able to avoid the phenomenon of multiple thimbles. In fact, there exists one and only one thimble for each sample member of the initial density matrix. We demonstrate the approach through explicitly computing the real-time propagator for an interacting scalar in 0+1 dimensions, and find very good convergence allowing for comparison with perturbation theory and the classical-statistical approximation to real-time dynamics.

Collective Jahn-Teller Interactions through Light-Matter Coupling in a Cavity.

The ultrafast nonradiative relaxation of a molecular ensemble coupled to a cavity mode is considered theoretically and by real-time quantum dynamics. For equal coupling strength of single molecules to the cavity mode, the nonradiative relaxation rate from the upper to the lower polariton states is found to strongly depend on the number of coupled molecules. The coupling of both bright and dark polaritonic states among each other constitutes a special case of (pseudo-)Jahn-Teller interactions involving collective displacements the internal coordinates of the molecules in the ensemble, and the strength of the first order vibronic coupling depends exclusively on the gradient of the energy gaps between molecular electronic states. For N>2 molecules, the N-1 dark light-matter states between the two optically active polaritons feature true collective conical intersection crossings, whose location depends on the internal atomic coordinates of each molecule in the ensemble, and which contribute to the ultrafast nonradiative decay from the upper polariton.

Modular path integral methodology for real-time quantum dynamics.

In a recent communication [N. Makri, J. Chem. Phys. 148, 101101 (2018)], it was shown that the locality of interactions in many systems of interest allows a decomposition of the path integral and its evaluation via sequential linking of the paths of relatively small "modules" (e.g., chemical groups or monomers). The present paper describes the modular path integral methodology for simulating dynamical properties by propagating the density matrix in real time. The procedure is first presented for the simple topology of a single-file arrangement of units interacting via nearest neighbor couplings and subsequently extended to the calculation of two-particle correlations in arrays that may also contain some long-range interactions, to the treatment of systems with side chains or cyclic structures, to the simulation of internal dynamics in long organic molecules, and to the modifications required for coupling of one or several units of a system to dissipative environments. Illustrative applications to the dynamics of interacting two-level-systems are presented.

Constrained quantum annealing of graph coloring

We investigate a quantum annealing approach based on real-time quantum dynamics for graph coloring. In this approach, a driving Hamiltonian is chosen so that constraints are naturally satisfied without penalty terms, and the dimension of the Hilbert space is considerably reduced. The total Hamiltonian, which consists of driving and problem Hamiltonians, resembles a disordered quantum spin chain. The ground state of the problem Hamiltonian for graph coloring is degenerate. This degeneracy is advantageous and is characteristic of this approach. Real-time quantum simulations in a small system demonstrate interesting results and provide some insight into quantum annealing.

Real Time Quantum Dynamics of Spontaneous Translational Symmetry Breakage in the Early Stage of Photo-Induced Structural Phase Transitions

Real time quantum dynamics of the spontaneous translational symmetry breakage in the early stage of photo-induced structural phase transitions is reviewed and supplementally explained, under the guide of the Toyozawa theory, which is exactly in compliance with the conservation laws of the total momentum and energy. At the Franck-Condon state, an electronic excitation just created by a visible light, is in a plane wave state, which is extended all over the crystal. While, after the lattice relaxation having been completed, it is localized around a certain lattice site of the crystal, as a new excitation. Is there a sudden shrinkage of the excitation wave function, in between? No! The wave function never shrinks, but only the spatial (or inter lattice-site) quantum coherence (interference) of the excitation disappears, as the lattice relaxation proceeds. This is nothing but the spontaneous breakage of translational symmetry.

Quench dynamics of a dissipative Rydberg gas in the classical and quantum regimes

Understanding the non-equilibrium behavior of quantum systems is a major goal of contemporary physics. Much research is currently focused on the dynamics of many-body systems in low-dimensional lattices following a quench, i.e., a sudden change of parameters. Already such a simple setting poses substantial theoretical challenges for the investigation of the real-time post-quench quantum dynamics. In classical many-body systems the Kolmogorov-Mehl-Johnson-Avrami model describes the phase transformation kinetics of a system that is quenched across a first order phase transition. Here we show that a similar approach can be applied for shedding light on the quench dynamics of an interacting gas of Rydberg atoms, which has become an important experimental platform for the investigation of quantum non-equilibrium effects. We are able to gain an analytic understanding of the time-evolution following a sudden quench from an initial state devoid of Rydberg atoms and identify strikingly different behaviors of the excitation growth in the classical and quantum regimes. Our approach allows us to describe quenches near a non-equilibrium phase transition and provides an approximate analytic solution deep in the quantum domain.

Quantum Monte Carlo tunneling from quantum chemistry to quantum annealing

Quantum Tunneling is ubiquitous across different fields, from quantum chemical reactions, and magnetic materials to quantum simulators and quantum computers. While simulating the real-time quantum dynamics of tunneling is infeasible for high-dimensional systems, quantum tunneling also shows up in quantum Monte Carlo (QMC) simulations that scale polynomially with system size. Here we extend a recent results obtained for quantum spin models {[{Phys. Rev. Lett.} {\bf 117}, 180402 (2016)]}, and study high-dimensional continuos variable models for proton transfer reactions. We demonstrate that QMC simulations efficiently recover ground state tunneling rates due to the existence of an instanton path, which always connects the reactant state with the product. We discuss the implications of our results in the context of quantum chemical reactions and quantum annealing, where quantum tunneling is expected to be a valuable resource for solving combinatorial optimization problems.

Real-Time Quantum Dynamics of Long-Range Electronic Excitation Transfer in Plasmonic Nanoantennas.

Using large-scale, real-time, quantum dynamics calculations, we present a detailed analysis of electronic excitation transfer (EET) mechanisms in a multiparticle plasmonic nanoantenna system. Specifically, we utilize real-time, time-dependent, density functional tight binding (RT-TDDFTB) to provide a quantum-mechanical description (at an electronic/atomistic level of detail) for characterizing and analyzing these systems, without recourse to classical approximations. We also demonstrate highly long-range electronic couplings in these complex systems and find that the range of these couplings is more than twice the conventional cutoff limit considered by Förster resonance energy transfer (FRET)-based approaches. Furthermore, we attribute these unusually long-ranged electronic couplings to the coherent oscillations of conduction electrons in plasmonic nanoparticles. This long-range nature of plasmonic interactions has important ramifications for EET; in particular, we show that the commonly used "nearest-neighbor" FRET model is inadequate for accurately characterizing EET even in simple plasmonic antenna systems. These findings provide a real-time, quantum-mechanical perspective for understanding EET mechanisms and provide guidance in enhancing plasmonic properties in artificial light-harvesting systems.

Periodic Airy process and equilibrium dynamics of edge fermions in a trap

We establish an exact mapping between (i) the equilibrium (imaginary time) dynamics of non-interacting fermions trapped in a harmonic potential at temperature T=1∕β and (ii) non-intersecting Ornstein–Uhlenbeck (OU) particles constrained to return to their initial positions after time β. Exploiting the determinantal structure of the process we compute the universal correlation functions both in the bulk and at the edge of the trapped Fermi gas. The latter corresponds to the top path of the non-intersecting OU particles, and leads us to introduce and study the time-periodic Airy2 process, A2b(u), depending on a single parameter, the period b. The standard Airy2 process is recovered for b=+∞. We discuss applications of our results to the real time quantum dynamics of trapped fermions.

Finite-temperature time-dependent variation with multiple Davydov states.

The Dirac-Frenkel time-dependent variational approach with Davydov Ansätze is a sophisticated, yet efficient technique to obtain an accurate solution to many-body Schrödinger equations for energy and charge transfer dynamics in molecular aggregates and light-harvesting complexes. We extend this variational approach to finite temperature dynamics of the spin-boson model by adopting a Monte Carlo importance sampling method. In order to demonstrate the applicability of this approach, we compare calculated real-time quantum dynamics of the spin-boson model with that from numerically exact iterative quasiadiabatic propagator path integral (QUAPI) technique. The comparison shows that our variational approach with the single Davydov Ansätze is in excellent agreement with the QUAPI method at high temperatures, while the two differ at low temperatures. Accuracy in dynamics calculations employing a multitude of Davydov trial states is found to improve substantially over the single Davydov Ansatz, especially at low temperatures. At a moderate computational cost, our variational approach with the multiple Davydov Ansatz is shown to provide accurate spin-boson dynamics over a wide range of temperatures and bath spectral densities.