Reduced Density Matrix For System Research Articles

New method for directly computing reduced density matrices

We demonstrate the power of a first principle-based and practicable method that allows for the perturbative computation of reduced density matrix elements of an open quantum system without making use of any master equations. The approach is based on techniques from non-equilibrium quantum field theory like thermo field dynamics, the Schwinger-Keldsyh formalism, and the Feynman-Vernon influence functional. It does not require the Markov approximation and is essentially a Lehmann-Szymanzik-Zimmermann-like reduction. In order to illustrate this method, we consider a real scalar field as an open quantum system interacting with an environment comprising another real scalar field. We give a general formula that allows for the perturbative computation of density matrix elements for any number of particles in a momentum basis. Finally, we consider a simple toy model and use this formula to obtain expressions for some of the system's reduced density matrix elements.

Quarkonium dynamics inside the Quark-Gluon Plasma using open quantum systems

In recent years, a significant theoretical effort has been made towards a dynamical description of quarkonia inside the Quark-Gluon Plasma (QGP), using the open quantum systems formalism. In this framework, one can get a real-time description of a quantum system (here the quarkonium) in interaction with a thermal bath (the QGP) by integrating out the bath degrees of freedom and studying the system reduced density matrix. We investigate the real-time dynamics of a correlated heavy quark-antiquark pair inside the QGP using a quantum master equation previously derived from first QCD principles in [4]. The full equation is directly resolved in 1D to lessen computing costs and is used for the first time to gain insight on the dynamics in both a static and evolving medium following a Björken-like temperature evolution.

Small Matrix Decomposition of Feynman Path Amplitudes.

The small matrix decomposition of the path integral (SMatPI) is employed to devise expressions for the quantum mechanical amplitude of forward-backward paths in the path integral formulation. The amplitude is expressed as a sum of small matrix products, whose size is equal to that of the system's reduced density matrix, allowing the treatment of composite systems consisting of interacting subunits without the large storage requirements of the full amplitude tensor. Representative applications on a four-spin system with the topology of the basic dendrimer block are presented.

Efficient Exploration of Hamiltonian Parameter Space for Optimal Control of Non-Markovian Open Quantum Systems.

We present a general method to efficiently design optimal control sequences for non-Markovian open quantum systems, and illustrate it by optimizing the shape of a laser pulse to prepare a quantum dot in a specific state. The optimization of control procedures for quantum systems with strong coupling to structured environments-where time-local descriptions fail-is a computationally challenging task. Wemodify the numerically exact time evolving matrix product operator (TEMPO) method, such that it allows the repeated computation of the time evolution of the reduced system density matrix for various sets of control parameters at very low computational cost. This method is potentially useful for studying numerous optimal control problems, in particular in solid state quantum devices where the coupling to vibrational modes is typically strong.

Efficient choice of colored noise in the stochastic dynamics of open quantum systems.

The stochastic Liouville-von Neumann (SLN) equation describes the dynamics of an open quantum system reduced density matrix coupled to a non-Markovian harmonic environment. The interaction with the environment is represented by complex colored noises which drive the system, and whose correlation functions are set by the properties of the environment. We present a number of schemes capable of generating colored noises of this kind that are built on a noise amplitude reduction procedure [Imai etal., Chem. Phys. 446, 134 (2015)CMPHC20301-010410.1016/j.chemphys.2014.11.014], including two analytically optimized schemes. In doing so, we pay close attention to the properties of the correlation functions in Fourier space, which we derive in full. For some schemes the method of Wiener filtering for deconvolutions leads to the realization that weakening causality in one of the noise correlation functions improves numerical convergence considerably, allowing us to introduce a well-controlled method for doing so. We compare the ability of these schemes, along with an alternative optimized scheme [Schmitz and Stockburger, Eur. Phys. J.: Spec. Top. 227, 1929 (2019)1951-635510.1140/epjst/e2018-800094-y], to reduce the growth in the mean and variance of the trace of the reduced density matrix, and their ability to extend the region in which the dynamics is stable and well converged for a range of temperatures. By numerically optimizing an additional noise scaling freedom, we identify the scheme which performs best for the parameters used, improving convergence by orders of magnitude and increasing the time accessible by simulation.

Equilibrium stationary coherence in the multilevel spin-boson model

Interaction between a quantum system and its environment can induce stationary coherences -- off-diagonal elements in the reduced system density matrix -- even at equilibrium. This work investigates the ``quantumness'' of such phenomena by examining the ability of classical and semiclassical models to describe equilibrium stationary coherence in the multi-level spin boson (MLSB) model, a common model for light-harvesting systems. A well justified classical harmonic oscillator model is found to fail to capture equilibrium coherence. This failure is attributed to the effective weakness of classical system-bath interactions due to the absence of a discrete system energy spectrum and, consequently, of quantized shifts in oscillator coordinates. Semiclassical coherences also vanish for a dimeric model with parameters typical of biological light-harvesting, i.e., where both system sites couple to the bath with the same reorganization energy. In contrast, equilibrium coherence persists in a fully quantum description of the same system, suggesting a uniquely quantum-mechanical origin for equilibrium stationary coherence in, e.g., photosynthetic systems. Finally, as a computational tool, a perturbative expansion is introduced that, at third order in $\hbar$, gives qualitatively correct behavior at ambient temperatures for all configurations examined.

Exactly thermalized quantum dynamics of the spin-boson model coupled to a dissipative environment

We present an application of the Extended Stochastic Liouville-von Neumann equations (ESLN) method introduced earlier [PRB 95, 125124 (2017); PRB 97, 224310 (2018)] which describes the dynamics of an exactly thermalised open quantum system reduced density matrix coupled to a non-Markovian harmonic environment. Critically, the combined system of the open system fully coupled to its environment is thermalised at finite temperature using an imaginary time evolution procedure before the application of real time evolution. This initialises the combined system in the correct canonical equilibrium state rather than being initially decoupled. We apply our theory to the spin-boson Hamiltonian and develop a number of competing ESLN variants designed to reduce the numerical divergence of the trace of the open system density matrix. We find that a careful choice of the driving noises is essential for improving numerical stability. We also investigate the effect of applying higher order numerical schemes for solving stochastic differential equations, such as the Stratonovich-Heun scheme, and conclude that stochastic sampling dominates convergence with the improvement associated with the numerical scheme being less important for short times but required for late times. To verify the method and its numerical implementation, we consider evolution under a fixed Hamiltonian and show that the system either remains in, or approaches, the correct canonical equilibrium state at long times. Additionally, evolution of the open system under non-equilibrium Landau-Zener (LZ) driving is considered and the asymptotic convergence to the LZ limit was observed for vanishing system-environment coupling and temperature. When coupling and temperature are non-zero, initially thermalising the combined system at a finite time in the past was found to be a better approximation of the true LZ initial state than a pure state.

Multi-level description of the vibronic dynamics of open quantum systems.

A new approximate coherent state path integral approach, which enables accurate and efficient dynamical treatment of model Hamiltonians that incorporate excited electronic states of multiple chromophores that are coupled to discrete high frequency harmonic vibrational modes, is presented. The approach is based on the mapping Hamiltonian formalism for the electronic states together with semiclassical coherent state expressions for the forward and backward propagators describing the quantum bath modes. The density matrix dynamics is propagated in the full coherent state basis for the electronic mapping and discrete vibrational mode oscillators using ensembles of weighted trajectories. An effective scheme for projecting the ensemble onto selected vibronic basis states is presented enabling the evolution of the reduced system density matrix to be monitored as well as exploring the importance of selected vibronic relaxation pathways in the multichromophore system dynamics. The approach is demonstrated for simple model Hamiltonians, and we show how this coherent state density matrix propagation approach for high frequency discrete harmonic vibrational modes can be combined with partial linearized density matrix propagation to treat an additional continuum bath of low frequency environmental modes that could, in principle, include anharmonicity.

Contributions to single-shot energy exchanges in open quantum systems.

The exchange of energy between a classical open system and its environment can be analyzed for a single run of an experiment using the phase-space trajectory of the system. By contrast, in the quantum regime such energy exchange processes must be defined for an ensemble of runs of the same experiment based on the reduced system density matrix. Single-shot approaches based on stochastic wave functions have been proposed for quantum systems that are continuously monitored or weakly coupled to a heat bath. However, for systems strongly coupled to the environment and not continuously monitored, a single-shot analysis has not been attempted because no system wave function exists for such systems within the standard formulation of quantum theory. Using the notion of the conditional wave function of a quantum system, we derive here an exact formula for the rate of total energy change in an open quantum system, valid for arbitrary coupling between the system and the environment. In particular, this allows us to identify three distinct contributions to the total energy flow: an external contribution coming from the explicit time dependence of the Hamiltonian, an interaction contribution associated with the interaction part of the Hamiltonian, and an entanglement contribution, directly related to the presence of entanglement between the system and its environment. Given the close connection between weak values and the conditional wave function, the approach presented here provides a new avenue for experimental studies of energy fluctuations in open quantum systems.

Time-Dependent Density Functional Theory for Open Systems and Its Applications.

Photovoltaic devices, electrochemical cells, catalysis processes, light emitting diodes, scanning tunneling microscopes, molecular electronics, and related devices have one thing in common: open quantum systems where energy and matter are not conserved. Traditionally quantum chemistry is confined to isolated and closed systems, while quantum dissipation theory studies open quantum systems. The key quantity in quantum dissipation theory is the reduced system density matrix. As the reduced system density matrix is an O(M! × M!) matrix, where M is the number of the particles of the system of interest, quantum dissipation theory can only be employed to simulate systems of a few particles or degrees of freedom. It is thus important to combine quantum chemistry and quantum dissipation theory so that realistic open quantum systems can be simulated from first-principles. We have developed a first-principles method to simulate the dynamics of open electronic systems, the time-dependent density functional theory for open systems (TDDFT-OS). Instead of the reduced system density matrix, the key quantity is the reduced single-electron density matrix, which is an N × N matrix where N is the number of the atomic bases of the system of interest. As the dimension of the key quantity is drastically reduced, the TDDFT-OS can thus be used to simulate the dynamics of realistic open electronic systems and efficient numerical algorithms have been developed. As an application, we apply the method to study how quantum interference develops in a molecular transistor in time domain. We include electron-phonon interaction in our simulation and show that quantum interference in the given system is robust against nuclear vibration not only in the steady state but also in the transient dynamics. As another application, by combining TDDFT-OS with Ehrenfest dynamics, we study current-induced dissociation of water molecules under scanning tunneling microscopy and follow its time dependent dynamics. Given the rapid development in ultrafast experiments with atomic resolution in recent years, time dependent simulation of open electronic systems will be useful to gain insight and understanding of such experiments. This Account will mainly focus on the practical aspects of the TDDFT-OS method, describing the numerical implementation and demonstrating the method with applications.

Extended hierarchy equation of motion for the spin-boson model.

An extended hierarchy equation of motion (HEOM) is proposed and applied to study the dynamics of the spin-boson model. In this approach, a complete set of orthonormal functions are used to expand an arbitrary bath correlation function. As a result, a complete dynamic basis set is constructed by including the system reduced density matrix and auxiliary fields composed of these expansion functions, where the extended HEOM is derived for the time derivative of each element. The reliability of the extended HEOM is demonstrated by comparison with the stochastic Hamiltonian approach under room-temperature classical ohmic and sub-ohmic noises and the multilayer multiconfiguration time-dependent Hartree theory under zero-temperature quantum ohmic noise. Upon increasing the order in the hierarchical expansion, the result obtained from the extended HOEM systematically converges to the numerically exact answer.

Variational mixed quantum/semiclassical simulation of dihalogen guest and rare-gas solid host dynamics.

A variational mixed quantum-semiclassical theory for the internal nuclear dynamics of a small molecule and the induced small-amplitude coherent motion of a low-temperature host medium is developed, tested, and used to simulate the temporal evolution of nonstationary states of the internal molecular and surrounding medium degrees of freedom. In this theory, termed the Fixed Vibrational Basis/Gaussian Bath (FVB/GB) method, the system is treated fully quantum mechanically while Gaussian wave packets are used for the bath degrees of freedom. An approximate time-dependent wave function of the entire model is obtained instead of just a reduced system density matrix, so the theory enables the analysis of the entangled system and bath dynamics that ensues following initial displacement of the internal-molecular (system) coordinate from its equilibrium position. The norm- and energy-conserving properties of the propagation of our trial wave function are natural consequences of the Dirac-Frenkel-McLachlan variational principle. The variational approach also stabilizes the time evolution in comparison to the same ansatz propagated under a previously employed locally quadratic approximation to the bath potential and system-bath interaction terms in the bath-parameter equations of motion. Dynamics calculations are carried out for molecular iodine in a 2D krypton lattice that reveal both the time-course of vibrational decoherence and the details of host-atom motion accompanying energy dissipation and dephasing. This work sets the stage for the comprehensive simulation of ultrafast time-resolved optical experiments on small molecules in low-temperature solids.

Decay dynamics in a strongly driven atom–molecule coupled system

Within the framework of master equation, we study decay dynamics of an atom–molecule system strongly coupled by two photoassociation lasers. Summing over the infinite number of electromagnetic vacuum modes that are coupled to the system, we obtain an integro-differential master equation for the system's reduced density matrix. We use this equation to describe correlated spontaneous emission from a pair of electronically excited diatomic ro-vibrational states. The temporal evolution of emitted radiation intensity shows quantum beats that result from the laser-induced coherence between the two excited states. The phase difference between the two driving fields is found to significantly affect the decay dynamics and the beats. Our results demonstrate the possibility to control decay and decoherence in the system by tuning the relative intensity and the phase between the two lasers. We further show that if the ground-state continuum has a shape resonance at a low energy, then the quantum beats show two distinctive time scales of oscillations in the strong coupling regime. One of the time scales originates from the energy gap between the two excited states while the other time scale corresponds to the collision energy at which free-bound Franck–Condon overlap is resonantly peaked due to the shape resonance.

Noncanonical statistics of a spin-boson model: Theory and exact Monte Carlo simulations

Equilibrium canonical distribution in statistical mechanics assumes weak system-bath coupling (SBC). In real physical situations this assumption can be invalid, and equilibrium quantum statistics of the system may be noncanonical. By exploiting both polaron transformation and perturbation theory in a spin-boson model, an analytical treatment is advocated to study noncanonical statistics of a two-level system at arbitrary temperature and for arbitrary SBC strength, yielding theoretical results in agreement with exact Monte Carlo simulations. In particular, the eigen-representation of system's reduced density matrix is used to quantify noncanonical statistics as well as the quantumness of the open system. For example, it is found that irrespective of SBC strength, noncanonical statistics enhances as temperature decreases but vanishes at high temperature.

Reduced density matrix hybrid approach: An efficient and accurate method for adiabatic and non-adiabatic quantum dynamics

We present a new approach to calculate real-time quantum dynamics in complex systems. The formalism is based on the partitioning of a system's environment into "core" and "reservoir" modes with the former to be treated quantum mechanically and the latter classically. The presented method only requires the calculation of the system's reduced density matrix averaged over the quantum core degrees of freedom which is then coupled to a classically evolved reservoir to treat the remaining modes. We demonstrate our approach by applying it to the spin-boson problem using the noninteracting blip approximation to treat the system and core, and Ehrenfest dynamics to treat the reservoir. The resulting hybrid methodology is accurate for both fast and slow baths, since it naturally reduces to its composite methods in their respective regimes of validity. In addition, our combined method is shown to yield good results in intermediate regimes where neither approximation alone is accurate and to perform equally well for both strong and weak system-bath coupling. Our approach therefore provides an accurate and efficient methodology for calculating quantum dynamics in complex systems.

Dissipative dynamics of superconducting hybrid qubit systems

We perform a theoretical study of composed superconducting qubit systems for the case of a coupled qubit configuration based on a hybrid qubit circuit made of both charge and phase qubits, which are coupled via a σx ⊗ σz interaction. We compute the system's eigen-energies in terms of the qubit transition frequencies and the strength of the inter-qubit coupling, and describe the sensitivity of the energy crossing/anti-crossing features to such coupling. We compute the hybrid system's dissipative dynamics for the cases of i) collective and ii) independent decoherence, whereby the system interacts with one common and two different baths of harmonic oscillators, respectively. The calculations have been performed within the Bloch-Redfield formalism and we report the solutions for the populations and the coherences of the system's reduced density matrix. The dephasing and relaxation rates are explicitly calculated as a function of the heat bath temperature.

A quantum trajectory description of decoherence

A complete theoretical treatment in many problems relevant to physics, chemistry, and biology requires considering the action of the environment over the system of interest. Usually the environment involves a relatively large number of degrees of freedom, this making the problem numerically intractable from a purely quantum-mechanical point of view. To overcome this drawback, a new class of quantum trajectories is proposed. These trajectories, based on the same grounds as Bohmian ones, are solely associated to the system reduced density matrix, since the evolution of the environment degrees of freedom is not considered explicitly. Within this approach, environment effects come into play through a time-dependent damping factor that appears in the system equations of motion. Apart from their evident computational advantage, this type of trajectories also results very insightful to understand the system decoherence. In particular, here we show the usefulness of these trajectories analyzing decoherence effects in interference phenomena, taking as a working model the well-known double-slit experiment.

Condensed-Phase Relaxation of Multilevel Quantum Systems. I. An Exactly Solvable Model

An analytically solvable model of multilevel condensed-phase quantum dynamics relevant to vibrational relaxation and electron transfer is presented. Exact solutions are derived for the reduced system density matrix dynamics of a degenerate N-level quantum system characterized by nearest-neighbor hopping and off-diagonal coupling (which is linear in the bath coordinates) to a harmonic oscillator bath. We demonstrate that for N> 2 the long-time steady-state system site occupation probabilities are not the same for all sites; that is, they are distributed in a non-Boltzmann manner, which depends on the initial conditions and the number of levels in the system. Although the system-bath Hamiltonian considered here is restricted in form, the availability of an exact solution enables us to study the model in all regions of an extensive parameter space.

Exact dynamics of a two-qubit system in a spin star environment

We derive the exact reduced dynamics of a central two-qubit system in a spin star configuration. The exact evolution of the reduced system density matrix is obtained and we compute the limit of an infinite number of environment spins. Initially pure states of the central system evolve into mixed ones and we determine the decoherence-free states of the model. The long-time behavior is studied, partial decoherence is shown to be a result of the coupling of the qubits to the environment, and entanglement evolution of the central system is investigated.

Exact solution of a model of condensed-phase electron transfer with non-Condon effects

Non-Condon effects are important in the analysis of electron transfer in many systems coupled to a condensed-phase environment. We detail a novel condensed-phase electron transfer Hamiltonian that extends the spin-boson model to account for non-Condon effects. We show that the relevant reduced system density matrix dynamics can be calculated exactly for a particular class of bath Hamiltonians and system-bath couplings. An explicit formula for the long-time behavior of these systems is derived. We show that they exhibit non-Boltzmann long-time behavior that is independent of temperature, and depends on the system Hamiltonian and the initial system density matrix.