Environmental Degrees Of Freedom Research Articles

Stabilization of Charge-Transfer Excited States in Biological Systems: A Computational Focus on the Special Pair in Photosystem II Reaction Centers.

Charge-transfer (CT) excited states play an important role in many biological processes. However, many computational approaches often inadequately address the equilibration effects of nuclear and environmental degrees of freedom on these states. One prominent example of systems in which CT states are of utmost importance is reaction centers (RC) in photosystems. Here we use a multiscale approach combined with time-dependent density functional theory to explore the lowest CT excited state of the special pair PD1-PD2 in the Photosystem II-RC of a cyanobacterium. We find that the nonequilibrium CT excited state resides near the Soret band, making an exciton the lowest-energy excited state. However, accounting for nuclear and state-specific dielectric equilibration along the CT potential energy surface (PES), the CT state PD1--PD2+ stabilizes energetically below the excitonic state. This underscores the crucial role of state-specific solvation in mapping the PES of CT states, as demonstrated in a simplified dimer model.

Holographic open quantum systems: toy models and analytic properties of thermal correlators

We present a unified picture of open quantum systems, the theory of a system probing a noisy thermal environment, distilling lessons learnt from previous holographic analyses. Our treatment is applicable both when the system is coupled to short-lived (Markovian), and long-lived (non-Markovian) environmental degrees of freedom. The thermal environment is modeled using an asymptotically AdS black hole, and the systems of interest are simple probe field theories. The effective stochastic dynamics of the system is governed by real-time thermal correlators, which we compute using the gravitational Schwinger-Keldysh (grSK) geometry. We describe the structure of arbitrary tree-level contact and exchange Witten diagrams in the grSK geometry. In particular, we argue, that all such diagrams reduce to integrals supported on a single copy of the exterior of the black hole. The integrand is obtained as a multiple discontinuity of a function comprising ingoing boundary-bulk propagators, monodromy functions which appear as radial Boltzmann weights, and vertex factors. These results allow us to deduce the analytic structure of real-time thermal n-point functions in holographic CFTs. We illustrate the general statements by a two-dimensional toy model, dual to fields in the BTZ background, which we argue captures many of the essential features of generic open holographic QFTs.

Measuring out-of-time-ordered correlation functions without reversing time evolution

Out-of-time-ordered correlation functions (OTOCs) play a crucial role in the study of thermalization, entanglement, and quantum chaos, as they quantify the scrambling of quantum information due to complex interactions. As a consequence of their out-of-time-ordered nature, OTOCs are difficult to measure experimentally. Here we propose an OTOC measurement protocol that does not rely on the reversal of time evolution and is easy to implement in a range of experimental settings. The protocol accounts for both pure and mixed initial states, and is applicable to systems that interact with environmental degrees of freedom. We demonstrate the application of our protocol by the characterization of scrambling in a periodically-driven spin that exhibits quantum chaos.

Do atoms age?

Time evolution generically entangles a quantum state with environmental degrees of freedom. The resulting increase in entropy changes the properties of that quantum system leading to “aging”. It is interesting to ask if this familiar property also applies to simple, single particle quantum systems such as the decay of a radioactive particle. We propose a test of such aging in an ion clock setup where we probe for temporal changes to the energies of the electronic state of an ion containing a radioactive nucleus. Such effects are absent in standard quantum mechanics and this test is thus a potent null test for violations of quantum mechanics. As a proof of principle, we show that these effects exist in causal non-linear modifications of quantum mechanics.

Non-equilibrium dynamics of a dissipative two-site Hubbard model simulated on IBM quantum computers

Many-body physics is one very well suited field for testing quantum algorithms and for finding working heuristics on present quantum computers. We have investigated the non-equilibrium dynamics of one- and two-electron systems, which are coupled to an environment that introduces decoherence and dissipation. In our approach, the electronic system is represented in the framework of a two-site Hubbard model while the environment is modelled by a spin bath. To simulate the non-equilibrium population probabilities of the different states on a quantum computer we have encoded the electronic states and environmental degrees of freedom into qubits and ancilla qubits (bath), respectively. The total evolution time was divided into short time intervals, during which the system evolves. After each of these time steps, the system interacts with ancilla qubits representing the bath in thermal equilibrium. We have specifically studied spin baths leading to both, unital and non-unital dynamics of the electronic system and have found that electron correlations clearly enhance the electron transfer rates in the latter case. For short time periods, the simulation on the quantum computer is found to be in very good agreement with the exact results if error mitigation methods are applied. Our method to simulate also non-unitary time-evolution on a quantum computer can be well extended to simulate electronic systems in correlated spin baths as well as in bosonic and fermionic baths.

Time-Dependent Approaches to Open Quantum Systems

Couplings of a system to other degrees of freedom (that is, environmental degrees of freedom) lead to energy dissipation when the number of environmental degrees of freedom is large enough. Here we discuss quantal treatments for such energy dissipation. To this end, we discuss two different time-dependent methods. One is to introduce an effective time-dependent Hamiltonian, which leads to a classical equation of motion as a relationship among expectation values of quantum operators. We apply this method to a heavy-ion fusion reaction and discuss the role of dissipation on the penetrability of the Coulomb barrier. The other method is to start with a Hamiltonian with environmental degrees of freedom and derive an equation which the system degree of freedom obeys. For this, we present a new efficient method to solve coupled-channels equations, which can be easily applied even when the dimension of the coupled-channels equations is huge.

Quantum impurity models coupled to Markovian and non-Markovian baths.

We develop a method to study quantum impurity models, small interacting quantum systems bilinearly coupled to an environment, in the presence of an additional Markovian quantum bath, with a generic nonlinear coupling to the impurity. We aim at computing the evolution operator of the reduced density matrix of the impurity, obtained after tracing out all the environmental degrees of freedom. First, we derive an exact real-time hybridization expansion for this quantity, which generalizes the result obtained in the absence of the additional Markovian dissipation and which could be amenable to stochastic sampling through diagrammatic Monte Carlo. Then, we obtain a Dyson equation for this quantity and we evaluate its self-energy with a resummation technique known as the noncrossing approximation. We apply this novel approach to a simple fermionic impurity coupled to a zero temperature fermionic bath and in the presence of Markovian pump, losses, and dephasing.

Charge and energy transfer in large molecular assemblies: Quantum state diffusion with an adaptive basis.

We show that the stochastic, wave-function based quantum state diffusion approach in combination with an adaptive basis is well suited to numerically treat the motion of an excitation in large molecular aggregates in the complicated regime where the transfer-time between molecules is comparable to the decoherence caused by environmental degrees of freedom.

Reaction coordinates and transition states in enzymatic catalysis

Enzymatic reactions are complex chemical processes taking place in complex dynamic environments. Theoretical characterization of these reactions requires the determination of the reaction coordinate and the transition state ensemble. This is not an easy task because many degrees of freedom may be involved in principle. We present recent efforts to find good enzymatic reaction coordinates and the implications of these findings in the interpretation of enzymatic efficiency. In particular, we analyze different strategies based on the use of minimum free energy paths and direct localization of the dividing surface on multidimensional free energy surfaces. Another strategy is based on the generation of reactive trajectories, using the transition path sampling method, from which transition state configurations can be harvested. Most of the applications carried out until now coincide to stress the change in the nature of the reaction coordinate, in terms of the participation of the chemical and environmental degrees of freedom, as the reaction advances. The degrees of freedom of the chemical system are dominant at the transition state while environmental participation can be more important at early or late stages of the process. WIREs Comput Mol Sci 2018, 8:e1329. doi: 10.1002/wcms.1329This article is categorized under: Structure and Mechanism > Computational Biochemistry and Biophysics Molecular and Statistical Mechanics > Free Energy Methods Software > Simulation Methods

Connections between ’t Hooft’s beables and canonical descriptions of dissipative systems

According to a proposal by ’t Hooft, information loss introduced by constraints in certain classical dissipative systems may lead to quantization. This scheme can be realized within the Bateman model of two coupled oscillators, one damped and one accelerated. In this paper we analyze the links of this approach to effective Hamiltonians where the environmental degrees of freedom do not appear explicitly but their effect leads to the same friction force appearing in the Bateman model. In particular, it is shown that by imposing constraints, the Bateman Hamiltonian can be transformed into an effective one expressed in expanding coordinates. This one can be transformed via a canonical transformation into Caldirola and Kanai’s effective Hamiltonian that can be linked to the conventional system-plus-reservoir approach, for example, in a form used by Caldeira and Leggett.

Dynamic Stark effect, light emission, and entanglement generation in a laser-driven quantum optical system

We calculate the emission spectra, the Glauber $g^{(2)}$ function, and the entanglement of formation for a few two-level emitters coupled to a single cavity mode and subject to an external laser-excitation. To evaluate these quantities we couple the system to environmental degrees of freedom which leads to dissipative dynamics. Because of the periodic time-dependence of the system Hamiltonian, the coefficients of the (Markovian) master equation are constant if Floquet states are used as the computational basis. Studying the emission spectra we show that the dynamic Stark effect, i.e., the shift of spectral lines, first appears in the second order of the laser intensity. For the Glauber function, we find clearly distinguished parameter regimes of super- and sub-Poissonian light emission and explain the additional features appearing for finite laser intensity in terms of the quasienergy spectrum of the driven emitter-cavity system. Finally, we analyze the temperature and emitter-cavity coupling regimes where entanglement among the emitters is generated, and show that the laser-excitation leads to a decrease of entanglement.

Colloquium: Non-Markovian dynamics in open quantum systems

The dynamical behavior of open quantum systems plays a key role in many applications of quantum mechanics, examples ranging from fundamental problems, such as the environment-induced decay of quantum coherence and relaxation in many-body systems, to applications in condensed matter theory, quantum transport, quantum chemistry and quantum information. In close analogy to a classical Markov process, the interaction of an open quantum system with a noisy environment is often modelled by a dynamical semigroup with a generator in Lindblad form, which describes a memoryless dynamics leading to an irreversible loss of characteristic quantum features. However, in many applications open systems exhibit pronounced memory effects and a revival of genuine quantum properties such as quantum coherence and correlations. Here, recent results on the rich non-Markovian quantum dynamics of open systems are discussed, paying particular attention to the rigorous mathematical definition, to the physical interpretation and classification, as well as to the quantification of memory effects. The general theory is illustrated by a series of examples. The analysis reveals that memory effects of the open system dynamics reflect characteristic features of the environment which opens a new perspective for applications, namely to exploit a small open system as a quantum probe signifying nontrivial features of the environment it is interacting with. This article further explores the various physical sources of non-Markovian quantum dynamics, such as structured spectral densities, nonlocal correlations between environmental degrees of freedom and correlations in the initial system-environment state, in addition to developing schemes for their local detection. Recent experiments on the detection, quantification and control of non-Markovian quantum dynamics are also discussed.

Effective field theory during inflation: Reduced density matrix and its quantum master equation

We study the power spectrum of super-Hubble fluctuations of an inflaton-like scalar field, the "system", coupled to another scalar field, the "environment" during de Sitter inflation. We obtain the reduced density matrix for the inflaton fluctuations by integrating out the environmental degrees of freedom. These are considered to be massless and conformally coupled to gravity as a \emph{proxy} to describe degrees of freedom that remain sub-Hubble all throughout inflation. The time evolution of the density matrix is described by a quantum master equation, which describes the decay of the vacuum state, the production of particles and correlated pairs and quantum entanglement between super and sub-Hubble degrees of freedom. The quantum master equation provides a non-perturbative resummation of secular terms from self-energy (loop) corrections to the inflaton fluctuations. In the case studied here these are Sudakov-type double logarithms which result in the \emph{decay} of the power spectrum of inflaton fluctuations upon horizon crossing with a concomitant violation of scale invariance. The reduced density matrix and its quantum master equation furnish a powerful non-perturbative framework to study the effective field theory of long wavelength fluctuations by tracing short wavelength degrees of freedom.

Geometric phase and quantum correlations for a bipartite two-level system

We calculate the geometric phase of a bipartite two-level system coupled to an external environment. We compute the correction to the unitary geometric phase through a kinematic approach. To this end, we analyse the reduced density matrix of the bipartite system after tracing over the environmental degrees of freedom, for arbitrary initial states of the composite system. In all cases considered, the correction to the unitary phase has a similar structure as a function of the degree of the entanglement of the initial state. In the case of a maximally entangled state (MES), the survival phase is only the topological phase, and there is no correction induced by the environments. Further, we compute the quantum discord and concurrence of the bipartite state and analyse possible relations among these quantities and the geometric phase acquired during the non-unitary system's evolution.

Efficient finite-time measurements under thermal regimes

Contrary to conventional quantum mechanics, which treats measurement as instantaneous, here we explore a model for finite-time measurement. The main two-level system interacts with the measurement apparatus in a Markovian way described by the Lindblad equation, and with an environment, which does not include the measuring apparatus. To analyse the environmental effects on the final density operator, we use the Redfield approach, allowing us to consider a non-Markovian noise. In the present hybrid theory, to trace out the environmental degrees of freedom, we use a previously-developed analytic method based on superoperator algebra and Nakajima-Zwanzig superoperators. Here, we analyse two types of system-environment interaction, phase and amplitude damping, which allows us to conclude that, in general, a finite-time quantum measurement performed during a certain period is more efficient than an instantaneous measurement performed at the end of it, because the rate of change of the populations is attenuated by the system-measurement apparatus interaction.

Transport signatures of Majorana quantum criticality realized by dissipative resonant tunneling

We consider theoretically the transport properties of a spinless resonant electronic level coupled to strongly dissipative leads, in the regime of circuit impedance near the resistance quantum. Using the Luttinger liquid analogy, one obtains an effective Hamiltonian expressed in terms of interacting Majorana fermions, in which all environmental degrees of freedom (leads and electromagnetic modes) are encapsulated in a single fermionic bath. General transport equations for this system are then derived in terms of the Majorana $T\text{-matrix}$. A perturbative treatment of the Majorana interaction term yields the appearance of a marginal, linear dependence of the conductance on temperature when the system is tuned to its quantum critical point, in agreement with recent experimental observations. We investigate in detail the different crossovers involved in the problem, and analyze the role of the interaction terms in the transport scaling functions. In particular, we show that single barrier scaling applies when the system is slightly tuned away from its Majorana critical point, strengthening the general picture of dynamical Coulomb blockade.

Effect of Localized Surface-Plasmon Mode on Exciton Transport and Radiation Emission in Carbon Nanotubes

We report on a general theoretical approach to study exciton transport and emission in a single-walled carbon nanotube (SWNT) in the presence of a localized surface-plasmon (SP) mode within a metal nanoparticle interacting via near-field coupling. We derive a set of quantum mechanical equations of motion and approximate rate equations that account for the exciton, SP, and the environmental degrees of freedom. The material equations are complemented by an expression for the radiated power that depends on the exciton and SP populations and coherences, allowing for an examination of the angular distribution of the emitted radiation that would be measured in experiment. Numerical simulations for a (6,5) SWNT and cone-shaped Ag metal tip (MT) have been performed using this methodology. Comparison with physical parameters shows that the near-field interaction between the exciton-SP occurs in a weak coupling regime, with the diffusion processes being much faster than the exciton-SP population exchange. In such a case, the effect of the exciton population transfer to the MT with its subsequent dissipation (i.e., the Förster energy transfer) is to modify the exciton steady state distribution while reducing the equilibration time for excitons to reach a steady sate distribution. We find that the radiation distribution is dominated by SP emission for a SWNT-MT separation of a few tens of nanometers due to the fast SP emission rate, whereas the exciton-SP coherences can cause its rotation.

Statistically preferred basis of an open quantum system: its relation to the eigenbasis of a renormalized self-Hamiltonian.

We study the problem of the basis of an open quantum system, under a quantum chaotic environment, which is preferred in view of its stationary reduced density matrix (RDM), that is, the basis in which the stationary RDM is diagonal. It is shown that, under an initial condition composed of sufficiently many energy eigenstates of the total system, such a basis is given by the eigenbasis of a renormalized self-Hamiltonian of the system, in the limit of large Hilbert space of the environment. Here, the renormalized self-Hamiltonian is given by the unperturbed self-Hamiltonian plus a certain average of the interaction Hamiltonian over the environmental degrees of freedom. Numerical simulations performed in two models, both with the kicked rotor as the environment, give results consistent with the above analytical predictions.

Dynamics of Open Quantum Systems Using Parametric Representation with Coherent States

Open quantum systems and their dynamics are usually studied in terms of reduced density matrices. This approach allows a nonsymmetric description, which is useful when one of the two subsystems is to be considered an environment, at the expense of a loss of information, as tracing out the environmental degrees of freedom is an irreversible process. This has a series of consequences which can be severe. In this work we present an alternative description, which is still nonsymmetric but yet exact: It is based on a parametric representation of composite systems, as obtained by introducing environmental coherent states, such that the principal system get to be described by a set of pure states parametrically dependent on environmental variables. The representation allows one to relate properties which typically arise in studying systems with parametrically dependent Hamiltonians, such as the emergence of geometrical phases, with features which specifically characterize open quantum systems, such as decoherence and entanglement generation.

Three-Pulse Photon Echo of Finite Numbers of Molecules: Single-Molecule Traces

In conventional bulk nonlinear spectroscopy, the contribution from molecules with different environmental conditions sometimes conceals the properties of interest and prevents the assessment of the heterogeneity of complex systems. This is especially true when exploring mechanisms of coherence loss in multicomponent systems [Ishizaki and Fleming, J. Phys. Chem. B 2011, 115, 6227]. To avoid this drawback of ensemble measurements and evaluate single-molecule behavior, a quantum theory is proposed to study the three-pulse photon echo signal of a two-level system in a bath and reveal the fluctuations inherent to single molecules. The current method takes advantage of the coherent state representation to understand the photon echo experiment in a wave function formalism rather than the reduced density matrix. Information regarding the environmental degrees of freedom (DoF) is explicitly encoded in the initial state of the system plus bath. The thermal fluctuations of the initial states induce variation of the photon echo signal, which is clearly different from the ensemble average echo signal. We use our formalism to demonstrate the recovery of the conventional ensemble response signal from the single-molecule signal.