arXiv subjects

Michael Thoss

Publications and source records attributed to Michael Thoss.

At least 37 records · Page 2Linked to original sources

arXiv2023

Current-induced bond rupture in single-molecule junctions: Effects of multiple electronic states and vibrational modes

Current-induced bond rupture is a fundamental process in nanoelectronic architectures such as molecular junctions and in scanning tunneling microscopy measurements of molecules at surfaces. The understanding of the underlying mechanisms is important for the design of molecular junctions that are stable at higher bias voltages and is a prerequisite for further developments in the field of current-induced chemistry. In this work, we analyse the mechanisms of current-induced bond rupture employing a recently developed method, which combines the hierarchical equations of motion approach in twin space with the matrix product state formalism, and allows accurate, fully quantum mechanical simulations of the complex bond rupture dynamics. Extending previous work [J. Chem. Phys. 154, 234702 (2021)], we consider specifically the effect of multiple electronic states and multiple vibrational modes. The results obtained for a series of models of increasing complexity show the importance of vibronic coupling between different electronic states of the charged molecule, which can enhance the dissociation rate at low bias voltages profoundly.

cond-mat.mes-hall↗

arXiv2023

Current-induced forces in nanosystems: A hierarchical equations of motion approach

A new approach to calculating current-induced forces in charge transport through nanosystems is introduced. Starting from the fully quantum mechanical hierarchical equations of motion formalism, a timescale separation between electronic and vibrational degrees of freedom is used to derive a classical Langevin equation of motion for the vibrational dynamics as influenced by current-induced forces, such as the electronic friction. The resulting form of the friction is shown to be equivalent to previously derived expressions. The numerical exactness of the hierarchical equations of motion approach, however, allows the investigation of transport scenarios with strong intrasystem and system-environment interactions. As a demonstration, the electronic friction of three example systems is calculated and analyzed: a single electronic level coupled to one classical vibrational mode, two electronic levels coupled to one classical vibrational mode, and a single electronic level coupled to both a classical and quantum vibrational mode.

cond-mat.mes-hall↗

arXiv2022

How an electrical current can stabilize a molecular nanojunction

The stability of molecular junctions under transport is of the utmost importance for the field of molecular electronics. This question is often addressed within the paradigm of current-induced heating of nuclear degrees of freedom or current-induced forces acting upon the nuclei. At the same time, an essential characteristic of the failure of a molecular electronic device is its changing conductance -- typically from a finite value for the intact device to zero for a device that lost its functionality. In this publication, we focus on the current-induced changes in the molecular conductance, which are inherent to molecular junctions at the limit of mechanical stability. We employ a numerically exact framework based on the hierarchical equations of motion approach, which treats both electronic and nuclear degrees of freedom on an equal footing and does not impose additional assumptions. Studying generic model systems for molecular junctions with dissociative potentials for a wide range of parameters spanning the adiabatic and the nonadiabatic regime, we find that molecular junctions that exhibit a decrease in conductance upon dissociation are more stable than junctions that are more conducting in their dissociated state. This represents a new mechanism that stabilizes molecular junctions under current. Moreover, we identify characteristic signatures in the current of breaking junctions related to the interplay between changes in the conductance and the nuclear configuration and show how these are related to properties of the leads rather than characteristics of the molecule itself.

cond-mat.mes-hall↗

arXiv2022

Nonadiabatic to Adiabatic Transition of Electron Transfer in Colloidal Quantum Dot Molecules

Electron transfer is an important and fundamental process in chemistry, biology and physics, and has received significant attention in recent years. Perhaps one of the most intriguing questions concerns with the realization of the transitions between nonadiabatic and adiabatic regimes of electron transfer, as the coupling (hybridization) energy, $J$, between the donor and acceptor is varied. Here, using colloidal quantum dot molecules, a new class of coupled quantum dot dimers, we computationally demonstrate how the hybridization energy between the donor and acceptor quantum dots can be tuned by simply changing the neck dimensions and/or the quantum dot size. This provides a handle to tune the electron transfer from the nonadiabatic over-damped Marcus regime to the coherent adiabatic regime in a single system, without changing the reorganization energy, $λ$, or the typical phonon frequency, $ω_c$. We develop an atomistic model to account for several donor and acceptor states and how they couple to the lattice vibrations, and utilize the Ehrenfest mean-field mixed quantum-classical method to describe the charge transfer dynamics as the nonadiabatic parameter, $γ$, is varied. We find that charge transfer rates increase by several orders of magnitude as the system is driven to the coherent, adiabatic limit, even at elevated temperatures, and delineate the inter-dot and torsional acoustic modes that couple most strongly to the charge transfer reaction coordinate.

cond-mat.mes-hall↗

arXiv2022

Quantifying the influence of the initial state on the dynamics of an open quantum system

A small system in contact with a macroscopic environment usually approaches an asymptotic state, determined only by some macroscopic properties of the environment such as the temperature or the chemical potential. In the long-time limit, the state of the small system is thus expected to be independent of its initial state. In some situations, however, the asymptotic state of the system is influenced by its initial state and some information about the initial state is kept for all times. Motivated by this finding, we propose a measure to quantify the influence of the initial state of an open system on its dynamics. Using this measure we derive conditions under which the asymptotic state exists and is unique. We demonstrate our concepts for the dynamics of the spin-boson model, identify three qualitatively different long-time behaviors, and discuss how they can be distinguished based on the proposed measure.

quant-ph↗

arXiv2022

Nonequilibrium dynamics in a spin valve with noncollinear magnetization

We utilize a hybrid quantum-classical equation of motion approach to investigate the spin dynamics and spin-transfer torque in a spin valve under bias voltage. We show that the interplay between localized classical magnetic moments and conduction electrons induces a complex effective exchange coupling between the magnetic layers. This leads to a declination of magnetizations from layers anisotropy axes even in equilibrium. Introducing a finite bias voltage triggers spin currents and related spin-transfer torques which further tilt the magnetizations and govern the relaxation processes of the spin dynamics. Analyzing different scenarios of the applied bias voltage, we show that symmetric and asymmetric voltage drops can lead to relaxation times of the spin dynamics that differ by several orders of magnitude at comparable charge currents. In both cases we observe resonant features, where the relaxation is boosted whenever the chemical potential of the leads matches the maxima in the density of the states of the spin-valve electrons.

cond-mat.mes-hall↗

arXiv2022

Nonadiabatic vibronic effects in single-molecule junctions: A theoretical study using the hierarchical equations of motion approach

The interaction between electronic and vibrational degrees of freedom is an important mechanism in nonequilibrium charge transport through molecular nanojunctions. While adiabatic polaron-type coupling has been studied in great detail, new transport phenomena arise for nonadiabatic coupling scenarios corresponding to a breakdown of the Born-Oppenheimer approximation. Employing the numerically exact hierarchical equations of motion approach, we analyze the effect of nonadiabatic electronic-vibrational coupling on electron transport in molecular junctions considering a series of models with increasing complexity. The results reveal a significant influence of nonadiabatic coupling on the transport characteristics and a variety of interesting effects, including negative differential conductance. The underlying mechanisms are analyzed in detail.

cond-mat.mes-hall↗

arXiv2022

Quantum thermodynamics of nonadiabatically driven systems: The effect of electron-phonon interaction

In this work we study the effects of nonadiabatic external driving on the thermodynamics of an electronic system coupled to two electronic leads and to a phonon mode, with and without damping. In the limit of slow driving, we establish nonadiabatic corrections to quantum thermodynamic quantities. In particular, we study the first-order correction to the electronic population, charge-current, and vibrational excitation using a perturbative expansion, and compare the results to the numerically exact hierarchical equations of motion (HEOM) approach. Furthermore, the HEOM analysis spans both the weak and strong system-bath coupling regime and the slow and fast driving limits. We show that the electronic friction and the nonadiabatic corrections to the charge-current provide a clear indicator for the Franck-Condon effect and for non-resonant tunneling processes. We also discuss the validity of the approximate quantum master equation approach and the benefits of using HEOM to study quantum thermodynamics out of equilibrium.

cond-mat.stat-mech↗

arXiv2022

Nonequilibrium reaction rate theory: Formulation and implementation within the hierarchical equations of motion approach

The study of chemical reactions in environments under nonequilibrium conditions has been of interest recently in a variety of contexts, including current-induced reactions in molecular junctions and scanning tunneling microscopy experiments. In this work, we outline a fully quantum mechanical, numerically exact approach to describe chemical reaction rates in such nonequilibrium situations. The approach is based on an extension of the flux correlation function formalism to nonequilibrium conditions and uses a mixed real and imaginary time hierarchical equations of motion approach for the calculation of rate constants. As a specific example, we investigate current-induced intramolecular proton transfer reactions in a molecular junction for different applied bias voltages and molecule-lead coupling strengths.

physics.chem-ph↗

arXiv2022

Hierarchical equations of motion approach to hybrid fermionic and bosonic environments: Matrix product state formulation in twin space

We extend the twin-space formulation of the hierarchical equations of motion approach in combination with the matrix product state representation (introduced in J. Chem. Phys. 150, 234102, [2019]) to nonequilibrium scenarios where the open quantum system is coupled to a hybrid fermionic and bosonic environment. The key ideas used in the extension are a reformulation of the hierarchical equations of motion for the auxiliary density matrices into a time-dependent Schrödinger-like equation for an augmented multi-dimensional wave function as well as a tensor decomposition into a product of low-rank matrices. The new approach facilitates accurate simulations of non-equilibrium quantum dynamics in larger and more complex open quantum systems. The performance of the method is demonstrated for a model of a molecular junction exhibiting current-induced mode-selective vibrational excitation.

cond-mat.mes-hall↗

arXiv2021

Theory of Chirality Induced Spin Selectivity: Progress and Challenges

We provide a critical overview of the theory of the chirality-induced spin selectivity (CISS) effect, i.e., phenomena in which the chirality of molecular species imparts significant spin selectivity to various electron processes. Based on discussions in a recently held workshop, and further work published since, we review the status of CISS effects - in electron transmission, electron transport, and chemical reactions. For each, we provide a detailed discussion of the state-of-the-art in theoretical understanding and identify remaining challenges and research opportunities.

cond-mat.mtrl-sci↗

arXiv2021

Efficient steady state solver for the hierarchical equations of motion approach: Formulation and application to charge transport through nanosystems

An iterative approach is introduced, which allows the efficient solution of the hierarchical equations of motion (HEOM) for the steady state of open quantum systems. The approach combines the method of matrix equations with an efficient preconditioning technique to reduce the numerical effort of solving the HEOM. Illustrative applications to simulate nonequilibrium charge transport in single-molecule junctions demonstrate the performance of the method.

cond-mat.mes-hall↗

arXiv2021

Interaction-driven dynamical quantum phase transitions in a strongly correlated bosonic system

We study dynamical quantum phase transitions (DQPTs) in the extended Bose-Hubbard model after a sudden quench of the nearest-neighbor interaction strength. Using the time-dependent density matrix renormalization group, we demonstrate that interaction-driven DQPTs can appear after quenches between two topologically trivial insulating phases -- a phenomenon that has so far only been studied between gapped and gapless phases. These DQPTs occur when the interaction strength crosses a certain threshold value that does not coincide with the equilibrium phase boundaries, which is in contrast to quenches that involve a change of topology. In order to elucidate the nonequilibrium excitations during the time evolution, we define a new set of string and parity order parameters. We find a close connection between DQPTs and these newly defined order parameters for both types of quenches. In the interaction-driven case, the order parameter exhibits a singularity at the time of the DQPT only when the quench parameter is close to the threshold value. Finally, the timescales of DQPTs are scrutinized and different kinds of power laws are revealed for the topological and interaction-driven cases.

cond-mat.quant-gas↗

arXiv2021

Nonequilibrium open quantum systems with multiple bosonic and fermionic environments: A hierarchical equations of motion approach

We present a hierarchical equations of motion approach, which allows a numerically exact simulation of nonequilibrium transport in general open quantum systems involving multiple macroscopic bosonic and fermionic environments. The performance of the method is demonstrated for a model of a nanosystem, which involves interacting electronic and vibrational degrees of freedom and is coupled to fermionic and bosonic baths. The results show the intricate interplay of electronic and vibrational degrees of freedom in this nonequilibrium transport scenario for both voltage and thermally driven transport processes. Furthermore, the use of importance criteria to improve the efficiency of the method is discussed.

cond-mat.stat-mech↗

arXiv2021

Unraveling current-induced dissociation mechanisms in single-molecule junctions

Understanding current-induced bond rupture in single-molecule junctions is both of fundamental interest and a prerequisite for the design of molecular junctions, which are stable at higher bias voltages. In this work, we use a fully quantum mechanical method based on the hierarchical quantum master equation approach to analyze the dissociation mechanisms in molecular junctions. Considering a wide range of transport regimes, from off-resonant to resonant, non-adiabatic to adiabatic transport, and weak to strong vibronic coupling, our systematic study identifies three dissociation mechanisms. In the weak and intermediate vibronic coupling regime, the dominant dissociation mechanism is stepwise vibrational ladder climbing. For strong vibronic coupling, dissociation is induced via multi-quantum vibrational excitations triggered either by a single electronic transition at high bias voltages or by multiple electronic transitions at low biases. Furthermore, the influence of vibrational relaxation on the dissociation dynamics is analyzed and strategies for improving the stability of molecular junctions are discussed.

cond-mat.mes-hall↗

arXiv2021

Localization dynamics in a centrally coupled system

In systems where interactions couple a central degree of freedom and a bath, one would expect signatures of the bath's phase to be reflected in the dynamics of the central degree of freedom. This has been recently explored in connection with many-body localized baths coupled with a central qubit or a single cavity mode -- systems with growing experimental relevance in various platforms. Such models also have an interesting connection with Floquet many-body localization via quantizing the external drive, although this has been relatively unexplored. Here we adapt the multilayer multiconfigurational time-dependent Hartree (ML-MCTDH) method, a well-known tree tensor network algorithm, to numerically simulate the dynamics of a central degree of freedom, represented by a $d$-level system (qudit), coupled to a disordered interacting 1D spin bath. ML-MCTDH allows us to reach $\approx 10^2$ lattice sites, a far larger system size than what is feasible with exact diagonalization or kernel polynomial methods. From the intermediate time dynamics, we find a well-defined thermodynamic limit for the qudit dynamics upon appropriate rescaling of the system-bath coupling. The spin system shows similar scaling collapse in the Edward-Anderson spin glass order parameter or entanglement entropy at relatively short times. At longer time scales, we see slow growth of the entanglement, which may arise from dephasing mechanisms in the localized system or long-range interactions mediated by the central degree of freedom. Similar signs of localization are shown to appear as well with unscaled system-bath coupling.

cond-mat.dis-nn↗

arXiv2021

Non-Markovian effects in the spin-boson model at zero temperature

We investigate memory effects in the spin-boson model using a recently proposed measure for non-Markovian behavior based on the information exchange between an open system and its environment. Employing the numerical exact multilayer multiconfguration time-dependent Hartree approach, we simulate the dynamics of the spin-boson model at zero temperature for a broad range of parameters. For a fast bath, i.e. in the scaling limit, we find non-Markovian dynamics for a coherently decaying spin at weak system-bath coupling, whereas memory effects are absent for stronger coupling in the regimes of incoherent decay and localization. If the time scales of system and bath are comparable, a complex, non-monotonic dependence of non-Markovianity on the system-bath coupling strength is observed.

quant-ph↗

arXiv2020

Current-induced dissociation in molecular junctions beyond the paradigm of vibrational heating: The role of anti-bonding electronic states

The interaction between electronic and nuclear degrees of freedom in single-molecule junctions is an essential mechanism, which may result in the current-induced rupture of chemical bonds. As such, it is fundamental for the stability of molecular junctions and for the applicability of molecular electronic devices. In this publication, we study current-induced bond rupture in molecular junctions using a numerically exact scheme, which is based on the hierarchical quantum master equation (HQME) method in combination with a discrete variable representation for the nuclear degrees of freedom. Employing generic models for molecular junctions with dissociative nuclear potentials, we identify distinct mechanisms leading to dissociation, namely the electronic population of anti-bonding electronic states and the current-induced heating of vibrational modes. Our results reveal that the latter plays a negligible role whenever the electronic population of anti-bonding states is energetically possible. Consequently, the significance of current-induced heating as a source for dissociation in molecular junctions involving an active anti-bonding state is restricted to the non-resonant transport regime, which reframes the predominant paradigm in the field of molecular electronics.

cond-mat.mes-hall↗