Electronic Decoherence Research Articles

Interplay between energy dissipation and reservoir-induced thermalization in nonequilibrium quantum nanodevices

A solid state electronic nanodevice is an intrinsically open quantum system, exchanging both energy with the host material and carriers with connected reservoirs. Its out-of-equilibrium behavior is determined by a non-trivial interplay between electronic dissipation and decoherence induced by inelastic processes within the device, and the coupling of the latter to metallic electrodes. We propose a unified description, based on the density matrix formalism, that accounts for both these aspects, enabling to predict various steady-state as well as ultrafast nonequilibrium phenomena, nowadays experimentally accessible. More specifically, we derive a generalized density-matrix equation, particularly suitable for the design and optimization of a wide class of electronic and optoelectronic quantum devices. The power and flexibility of this approach is demonstrated with the application to a photoexcited triple-barrier nanodevice.

Reduced purities as measures of decoherence in many-electron systems

A hierarchy of measures of decoherence for many-electron systems that is based on the purity and the hierarchy of reduced electronic density matrices is presented. These reduced purities can be used to characterize electronic decoherence in the common case when the many-body electronic density matrix is not known and only reduced information about the electronic subsystem is available. Being defined from reduced electronic quantities, the interpretation of the reduced purities is more intricate than the usual (many-body) purity. This is because the nonidempotency of the r-body reduced electronic density matrix that is the basis of the reduced purity measures can arise due to decoherence or due to electronic correlations. To guide the interpretation, explicit expressions are provided for the one-body and two-body reduced purities for a general electronic state. Using them, the information content and structure of the one-body and two-body reduced purities is established, and limits on the changes that decoherence can induce are elucidated. The practical use of the reduced purities to understand decoherence dynamics in many-electron systems is exemplified through an analysis of the electronic decoherence dynamics in a model molecular system.

Investigation of the molecular mechanisms of electronic decoherence within a quinone cofactor

The notion of decoherence is particularly adapted to discuss the quantum-to-classical transition in the context of chemical reactions. Decoherence can be modeled by computing the time evolution of nuclear wave packets evolving on distinct potential energy surfaces, here using density functional theory (DFT) and Born–Oppenheimer molecular dynamics simulations. We investigate a redox cofactor of biological interest (tryptophan tryptophylquinone, TTQ) found in the enzyme methylamine dehydrogenase. We also report the first systematic comparison of semi-empirical DFT (tight-binding DFT) and classical force field approaches for estimating decoherence in molecular systems. In the TTQ cofactor, we find that decoherence combines structural and dynamical aspects: it is initiated by the divergent motions of few atoms and then propagates dynamically to the remaining atoms. It is the mass effect of all the atoms that leads to decoherence within a few femtosecond.

Optical probing of ultrafast electronic decay in Bi and Sb with slow phonons.

Illumination with laser sources leads to the creation of excited electronic states of particular symmetries, which can drive isosymmetric vibrations. Here, we use a combination of ultrafast stimulated and cw spontaneous Raman scattering to determine the lifetime of A(1g) and E(g) electronic coherences in Bi and Sb. Our results both shed new light on the mechanisms of coherent phonon generation and represent a novel way to probe extremely fast electron decoherence rates. The E(g) state, resulting from an unequal distribution of carriers in three equivalent band regions, is extremely short lived. Consistent with theory, the lifetime of its associated driving force reaches values as small as 2 (6) fs for Bi (Sb) at 300 K.

Two-Dimensional Electronic Spectroscopy of a Model Dimer System

Two-dimensional spectra of a dimer were measured to determine the timescale for electronic decoherence at room temperature. Anti-correlated beats in the crosspeaks were observed only during the period corresponding to the measured homogeneous lifetime.

Spectral Narrowing of UV-Visible Absorption and Emission Spectra of Anthracene-Derivatives in β-Cyclodextrin Nanocavity: Effects of Host/Guest Stoichiometry

Cyclodextrins (CD) are cyclic oligosaccharides consisting of six or more D-glucopyranose units, the interior of which forms a hydrophobic cavity. In the present study, we employed the CD confinement effects as a tool to suppress an electronic decoherence of guest wavefunction by reducing intermolecular interactions between a guest molecule and the surrounding environment. Effects of host/guest stoichiometry on the decoherence suppresion were investigated by comparing native β-CD with trimethyl-β-CD that should form only a 1:1 complex. Both fluorecence and fluorecence-excitation spectra of inclusion complexes exhibited spectral narrowings only for the β-CD host, suggesting that the formation of barrel-type β-CD dimer plays a key role for the pronounced spectral narrowings.

Electronic coherence dynamics in trans-polyacetylene oligomers

Electronic coherence dynamics in trans-polyacetylene oligomers are considered by explicitly computing the time dependent molecular polarization from the coupled dynamics of electronic and vibrational degrees of freedom in a mean-field mixed quantum-classical approximation. The oligomers are described by the Su-Schrieffer-Heeger Hamiltonian and the effect of decoherence is incorporated by propagating an ensemble of quantum-classical trajectories with initial conditions obtained by sampling the Wigner distribution of the nuclear degrees of freedom. The electronic coherence of superpositions between the ground and excited and between pairs of excited states is examined for chains of different length, and the dynamics is discussed in terms of the nuclear overlap function that appears in the off-diagonal elements of the electronic reduced density matrix. For long oligomers the loss of coherence occurs in tens of femtoseconds. This time scale is determined by the decay of population into other electronic states through vibronic interactions, and is relatively insensitive to the type and class of superposition considered. By contrast, for smaller oligomers the decoherence time scale depends strongly on the initially selected superposition, with superpositions that can decay as fast as 50 fs and as slow as 250 fs. The long-lived superpositions are such that little population is transferred to other electronic states and for which the vibronic dynamics is relatively harmonic.

Electron scattering by random adsorbates: A tunable decoherence mechanism in surface bands

AbstractMechanisms of electron decoherence at surfaces are manifold as they may originate from the various complex interactions of electrons with the static crystal structure and dynamical degrees of freedom of the environment. Decoherence effects manifest themselves in the spectroscopic data in a convoluted fashion and it is usually hard or even impossible to fully disentangle them from each other because of the lack of control of underlying mechanisms by the external observer. However, electronic propagation in quasi‐two‐dimensional image potential bands (IS‐bands) on flat low index surfaces of some metals is subject to an efficient decoherence mechanism that can be controlled externally by careful preparation of the surface. By dosing the concentration (i.e. the coverage) of adsorbates on clean surfaces, which act as randomly distributed scattering centres, one can tune the strength of incoherent IS‐electron scattering from defects. Such processes in IS‐bands on Cu(100) surface have been investigated by two‐photon‐photoemission (2PPE) spectroscopy and interpreted using Fermi golden rule approach to calculation of the quasiparticle decay rates and scattering cross sections. However, these results could reproduce the experimental data only in a limited energy interval. Here, we employ the description of electron decoherence in IS‐bands based on the propagator approach and infrared renormalization of quasiparticle self‐energy and demonstrate that it gives a very good agreement between the theoretical and experimental results for the cross sections. This enables us to discuss the temporal stages of electron dynamics and decoherence in the intermediate states of 2PPE spectroscopy of surface bands.

Detailed model study of dissipative quantum dynamics of K2 attached to helium nanodroplets

We thoroughly investigate vibrational quantum dynamics of dimers attached to He droplets, motivated by recent measurements with K2 (Claas et al 2006 J. Phys. B: At. Mol. Opt. Phys.39 S1151). For those femtosecond pump–probe experiments, the crucial observed features are not reproduced by gas-phase calculations, but agreement is found using a description based on dissipative quantum dynamics, as briefly shown in the work by Schlesinger et al (2010 Chem. Phys. Lett.490 245–8). Here we present a detailed study of the influence of possible effects induced by the droplet. The helium droplet causes electronic decoherence, shifts of potential surfaces and relaxation of wave packets in attached dimers. Moreover, a realistic description of (stochastic) desorption of dimers off the droplet needs to be taken into account. Step by step, we include and study the importance of these effects in our full quantum calculation of the effective dimer dynamics. This approach allows us to reproduce and explain all major experimental findings. We find that desorption is fast and occurs within 2–10 ps after electronic excitation. A further finding is that slow vibrational motion in the ground state can be considered frictionless.

Conical Intersections in an Ultracold Gas

We find that energy surfaces of more than two atoms or molecules interacting via transition dipole-dipole potentials generically possess conical intersections (CIs). Typically only few atoms participate strongly in such an intersection. For the fundamental case, a circular trimer, we show how the CI affects adiabatic excitation transport via electronic decoherence or geometric phase interference. These phenomena may be experimentally accessible if the trimer is realized by light alkali atoms in a ring trap, whose interactions are induced by off-resonant dressing with Rydberg states. Such a setup promises a direct probe of the full many-body density dynamics near a CI.

Intrinsic coherence dynamics and phase localization in nanoscale Aharonov-Bohm interferometers

The nonequilibrium real-time dynamics of electron decoherence is explored in the quantum transport through the nanoscale double-dot Aharonov-Bohm interferometers. We solve the exact master equation to find the exact quantum state of the device, from which the changes of the electron coherence through the magnetic flux in the nonequilibrium transport processes is obtained explicitly. We find that the relative phase between the two charge states of the degenerate double dot localizes to π 2 or − π for all different magnetic fluxes, due to decoherence. This nontrivial decoherence process can be manifested in the measurable occupation numbers.

Coulomb interaction effects and electron spin relaxation in the one-dimensional Kondo lattice model

We study the effects of the Coulomb interaction in the one dimensional Kondo lattice model on the phase diagram, the static magnetic susceptibility and electron spin relaxation. We show that onsite Coulomb interaction supports ferromagnetic order and nearest neighbor Coulomb interaction drives, depending on the electron filling, either a paramagnetic or ferromagnetic order. Furthermore we calculate electron quasiparticle life times, which can be related to electron spin relaxation and decoherence times, and explain their dependence on the strength of interactions and the electron filling in order to find the sweet spot of parameters where the relaxation time is maximized. We find that effective exchange processes between the electrons dominate the spin relaxation and decoherence rate.

Exploring dynamical electron theory beyond the Born–Oppenheimer framework: from chemical reactivity to non-adiabatically coupled electronic and nuclear wavepackets on-the-fly under laser field

Chemical theory and its application to dynamical electrons in molecules under intense electromagnetic fields is explored, in which we take an explicit account of nuclear nonadiabatic (kinematic) interactions along with simultaneous coupling with intense optical interactions. All the electronic wavefunctions studied here are necessarily time-dependent, and thereby beyond stationary state quantum chemistry based on the Born-Oppenheimer framework. As a general and tractable alternative framework with which to track the electronic and nuclear simultaneous dynamics, we propose an on-the-fly method to calculate the electron and nuclear wavepackets coupled along the branching non-Born-Oppenheimer paths, through which their bifurcations, strong quantum entanglement between nuclear electronic motions, and coherence and decoherence among the phases associated with them are properly represented. Some illustrative numerical examples are also reported, which are aimed at our final goals; real time tracking of nonadiabatic electronic states, chemical dynamics in densely degenerate electronic states coupled with nuclear motions and manipulation and/or creation of new electronic states in terms of intense lasers, and so on. Other examples are also presented as to how the electron wavepacket dynamics can be used to analyze chemical reactions, shedding a new light on some typical and conventional chemical reactions such as proton transfer followed by tautomerization.

Dynamics of quantum wave packets in complex molecules traced by 2D coherent electronic correlation spectroscopy

Electronic and nuclear molecular wavepackets are a clear manifestation of the wavelike properties of matter at the very heart of quantum mechanics. In this work we demonstrate how electronic two-dimensional spectroscopy (2D) serves as a highly evolved tool for the simultaneous investigation of both phenomena. In further analysis and theoretical treatments, 2D spectra form an ideal basis for the discussion of electronic decoherence, vibrational relaxation and electron-phonon coupling.

Coherence of nitrogen-vacancy electronic spin ensembles in diamond

We present an experimental and theoretical study of electronic spin decoherence in ensembles of nitrogen-vacancy (NV) color centers in bulk high-purity diamond at room temperature. Under appropriate conditions, we find ensemble NV spin coherence times (T_2) comparable to that of single NVs, with T_2 > 600 microseconds for a sample with natural abundance of 13C and paramagnetic impurity density ~10^15 cm^(-3). We also observe a sharp decrease of the coherence time with misalignment of the static magnetic field relative to the NV electronic spin axis, consistent with theoretical modeling of NV coupling to a 13C nuclear spin bath. The long coherence times and increased signal-to-noise provided by room-temperature NV ensembles will aid many applications of NV centers in precision magnetometry and quantum information.

Weak localization, Aharonov-Bohm oscillations, and decoherence in arrays of quantum dots

Combining scattering matrix theory with the non-linear σ-model and the Keldysh technique, we develop a unified theoretical approach for non-perturbative study of the effect of electron-electron interactions on weak localization and Aharonov-Bohm oscillations in arbitrary arrays of quantum dots. Our model embraces weakly disordered conductors, strongly disordered conductors, and metallic quantum dots. In all these cases, as T→0 the electron decoherence time saturates to a finite value determined by a universal formula which agrees quantitatively with a number of experiments. Our analysis provides overwhelming evidence in favor of electron-electron interactions as a universal mechanism for zero temperature electron decoherence in disordered conductors.

Quantum-classical description of environmental effects on electronic dynamics at conical intersections

Quantum-classical Liouville theory is used to simulate the dynamics of systems containing conical intersections. In particular quantum dynamical effects on the electronic population transfer and coherence in a quantum subsystem that arise from the presence of an environment are studied. The environment, in turn, is partitioned into an immediate environment representing, say, local molecular vibrations, and a bath representing other degrees of freedom. Population transfer may be enhanced or suppressed, depending on the relative values of the characteristic frequencies of the immediate environment and bath. Electronic decoherence and the destruction of geometric phase effects were observed for bath frequencies that are large relative to the molecular vibrations. The dynamics at higher dimensional conical intersections was found to be very sensitive to the environmental coupling. When a single collective solvent coordinate couples directly to the electronic subsystem, the characteristic frequency of the new coordinate, relative to that of the nuclear vibrational modes, has a strong effect on the population dynamics. The results also serve as a test of the QCL dynamical scheme for future applications to more detailed molecular descriptions of condensed phase environments for conical intersection dynamics.

Long-lived coherence in carotenoids

We use two-colour vibronic coherence spectroscopy to observe long-lived vibrational coherences in the ground electronic state of carotenoid molecules, with decoherence times in excess of 1 ps. Lycopene and spheroidene were studied isolated in solution, and within the LH2 light-harvesting complex extracted from purple bacteria. The vibrational coherence time is shown to increase significantly for the carotenoid in the complex, providing further support to previous assertions that long-lived electronic coherences in light-harvesting complexes are facilitated by in-phase motion of the chromophores and surrounding proteins. Using this technique, we are also able to follow the evolution of excited state coherences and find that for carotenoids in the light-harvesting complex the ⟨S2|S0⟩ superposition remains coherent for more than 70 fs. In addition to the implications of this long electronic decoherence time, the extended coherence allows us to observe the evolution of the excited state wavepacket. These experiments reveal an enhancement of the vibronic coupling to the first vibrational level of the C–C stretching mode and/or methyl-rocking mode in the ground electronic state 70 fs after the initial excitation. These observations open the door to future experiments and modelling that may be able to resolve the relaxation dynamics of carotenoids in solution and in natural light-harvesting systems.

Simulating quantum search algorithm using vibronic states of I2 manipulated by optimally designed gate pulses

In this paper, molecular quantum computation is numerically studied with the quantum search algorithm (Grover's algorithm) by means of optimal control simulation. Qubits are implemented in the vibronic states of I2, while gate operations are realized by optimally designed laser pulses. The methodological aspects of the simulation are discussed in detail. We show that the algorithm for solving a gate pulse-design problem has the same mathematical form as a state-to-state control problem in the density matrix formalism, which provides monotonically convergent algorithms as an alternative to the Krotov method. The sequential irradiation of separately designed gate pulses leads to the population distribution predicted by Grover's algorithm. The computational accuracy is reduced by the imperfect quality of the pulse design and by the electronic decoherence processes that are modeled by the non-Markovian master equation. However, as long as we focus on the population distribution of the vibronic qubits, we can search a target state with high probability without introducing error-correction processes during the computation. A generalized gate pulse-design scheme to explicitly include decoherence effects is outlined, in which we propose a new objective functional together with its solution algorithm that guarantees monotonic convergence.

Wigner-Boltzmann Monte Carlo approach to nanodevice simulation: from quantum to semiclassical transport

In this paper, we review and extend our recent works based on the Monte Carlo method to solve the Wigner-Boltzmann transport equation and model semiconductor nanodevices. After presenting the different possible approaches to quantum mechanical modelling, the formalism and the theoretical framework are described together with the particle Monte Carlo implementation using a technique fully compatible with semiclassical simulation. Examples are given to highlight the importance of considering both quantum and scattering effects in nanodevices operating at room temperature, such as resonant tunnelling diode (RTD), double-gate MOSFET and carbon nanotube FET. Quantum and semiclassical approaches are compared for transistor simulation. Finally, the phonon-induced electron decoherence in RTD and MOSFET is examined through the analysis of the density matrix elements computed from the Wigner function. This formalism is shown to be relevant for the quantitative analysis of devices operating in mixed quantum/semiclassical regime and to understand the transition between both regimes or between coherent and sequential tunnelling processes.