Thermal transport in fullerene-based molecular junctions: molecular dynamics simulations.

We investigate phonon thermal transport of fullerene-based single-molecule junctions by employing classical molecular dynamics (MD) simulations. We compute the thermal conductances of C60fullerene monomers, dimers, and trimers utilizing three distinct MD methods. We observe the equilibration dynamics in one approach, and employ two other nonequilibrium steady state simulation methods. We discuss technical aspects of each simulation technique, and show that their predictions for the thermal conductance agree. Our simulations reveal that while the thermal conductance of fullerene monomer and dimer junctions remains similar, that of trimer junctions experiences a significant reduction. This study could assist in the design of high-performing thermoelectric junctions, where low thermal conductance is desired.

Challenges in molecular dynamics simulations of heat exchange statistics.

We study heat exchange in temperature-biased metal-molecule-metal molecular junctions by employing the molecular dynamics simulator LAMMPS. Generating the nonequilibrium steady state with Langevin thermostats at the boundaries of the junction, we show that the average heat current across a gold-alkanedithiol-gold nanojunction behaves physically, with the thermal conductance value matching the literature. In contrast, the full probability distribution function for heat exchange, as generated by the simulator, violates the fundamental fluctuation symmetry for entropy production. We trace this failure back to the implementation of the thermostats and the expression used to calculate the heat exchange. To rectify this issue and produce the correct statistics, we introduce single-atom thermostats as an alternative to conventional many-atom thermostats. Once averaging heat exchange over the hot and cold thermostats, this approach successfully generates the correct probability distribution function, which we use to study the behavior of both the average heat current and its noise. We further examine the thermodynamic uncertainty relation in the molecular junction and show that it holds, albeit demonstrating nontrivial trends. Our study points to the need to carefully implement nonequilibrium molecular dynamics solvers in atomistic simulation software tools for future investigations of noise phenomena in thermal transport.

Delta-T Flicker Noise Demonstrated with Molecular Junctions.

Electronic flicker noise is recognized as the most abundant noise in electronic conductors, either as an unwanted contribution or as a source of information on electron transport mechanisms and material properties. This noise is typically observed when a voltage difference is applied across a conductor or current is flowing through it. Here, we identify an unknown type of electronic flicker noise that is found when a temperature difference is applied across a nanoscale conductor in the absence of a net charge current or voltage bias. The revealed delta-T flicker noise is demonstrated in molecular junctions and characterized using quantum transport theory. This noise is expected to arise in nanoscale electronic conductors subjected to unintentional temperature gradients, where it can be a performance-limiting factor. On the positive side, delta-T flicker noise can detect temperature differences across a large variety of nanoscale conductors, down to atomic-scale junctions with no special setup requirements.

Random walks on modular chains: Detecting structure through statistics.

We study kinetic transport through one-dimensional modular networks consisting of alternating domains using both analytical and numerical methods. We demonstrate that the mean velocity is insensitive to the local structure of the network, and it depends only on global, structural-averaged properties. However, by examining high-order cumulants characterizing the kinetics, we reveal information on the degree of inhomogeneity of blocks and the size of repeating units in the network. Specifically, in unbiased diffusion, the kurtosis is the first transport coefficient that exposes structural information, whereas in biased chains, the diffusion coefficient already reveals structural motifs. Nevertheless, this latter dependence is weak, and it disappears at both low and high biasing. Our study demonstrates that high-order moments of the population distribution over sites provide information about the network structure that is not captured by the first moment (mean velocity) alone. These results are useful towards deciphering mechanisms and determining architectures underlying long-range charge transport in biomolecules and biological and chemical reaction networks.

Hyperacceleration of quantum thermalization dynamics by bypassing long-lived coherences: An analytical treatment.

We develop a perturbative technique for solving Markovian quantum dissipative dynamics, with the perturbation parameter being a small gap in the eigenspectrum. As an example, we apply the technique and straightforwardly obtain analytically the dynamics of a three-level system with quasidegenerate excited states, where quantum coherences persist for very long times, proportional to the inverse of the energy splitting squared. We then show how to bypass this long-lived coherent dynamics and accelerate the relaxation to thermal equilibration in a hyper-exponential manner, a Markovian quantum-assisted Mpemba-like effect. This hyperacceleration of the equilibration process manifests if the initial state is carefully prepared, such that its coherences precisely store the amount of population relaxing from the initial condition to the equilibrium state. Our analytical method for solving quantum dissipative dynamics readily provides equilibration timescales, and as such it reveals how coherent and incoherent effects interlace in the dynamics. It further advises on how to accelerate relaxation processes, which is desirable when long-lived quantum coherences stagnate dynamics.

Full counting statistics and coherences: Fluctuation symmetry in heat transport with the unified quantum master equation.

Recently, a "unified" quantum master equation was derived and shown to be of the Gorini-Kossakowski-Lindblad-Sudarshan form. This equation describes the dynamics of open quantum systems in a manner that forgoes the full secular approximation and retains the impact of coherences between eigenstates close in energy. We implement full counting statistics with the unified quantum master equation to investigate the statistics of energy currents through open quantum systems with nearly degenerate levels. We show that, in general, this equation gives rise to dynamics that satisfy fluctuation symmetry, a sufficient condition for the Second Law of Thermodynamics at the level of average fluxes. For systems with nearly degenerate energy levels, such that coherences build up, the unified equation is simultaneously thermodynamically consistent and more accurate than the fully secular master equation. We exemplify our results for a "V" system facilitating energy transport between two thermal baths at different temperatures. We compare the statistics of steady-state heat currents through this system as predicted by the unified equation to those given by the Redfield equation, which is less approximate but, in general, not thermodynamically consistent. We also compare results to the secular equation, where coherences are entirely abandoned. We find that maintaining coherences between nearly degenerate levels is essential to properly capture the current and its cumulants. On the other hand, the relative fluctuations of the heat current, which embody the thermodynamic uncertainty relation, display inconsequential dependence on quantum coherences.

Simulations of heat transport in single-molecule junctions: Investigations of the thermal diode effect.

With the objective of understanding microscopic principles governing thermal energy flow in nanojunctions, we study phononic heat transport through metal-molecule-metal junctions using classical molecular dynamics (MD) simulations. Considering a single-molecule gold-alkanedithiol-gold junction, we first focus on aspects of method development and compare two techniques for calculating thermal conductance: (i) The Reverse Nonequilibrium MD (RNEMD) method, where heat is inputted and extracted at a constant rate from opposite metals. In this case, the thermal conductance is calculated from the nonequilibrium temperature profile that is created at the junction. (ii) The Approach-to-Equilibrium MD (AEMD) method, with the thermal conductance of the junction obtained from the equilibration dynamics of the metals. In both methods, simulations of alkane chains of a growing size display an approximate length-independence of the thermal conductance, with calculated values matching computational and experimental studies. The RNEMD and AEMD methods offer different insights, and we discuss their benefits and shortcomings. Assessing the potential application of molecular junctions as thermal diodes, alkane junctions are made spatially asymmetric by modifying their contact regions with the bulk, either by using distinct endgroups or by replacing one of the Au contacts with Ag. Anharmonicity is built into the system within the molecular force-field. We find that, while the temperature profile strongly varies (compared with the gold-alkanedithiol-gold junctions) due to these structural modifications, the thermal diode effect is inconsequential in these systems-unless one goes to very large thermal biases. This finding suggests that one should seek molecules with considerable internal anharmonic effects for developing nonlinear thermal devices.

Long-range charge transport in homogeneous and alternating-rigidity chains.

We study the interplay of intrinsic-electronic and environmental factors in long-range charge transport across molecular chains with up to N ∼ 80 monomers. We describe the molecular electronic structure of the chain with a tight-binding Hamiltonian. Thermal effects in the form of electron decoherence and inelastic scattering are incorporated with the Landauer-Büttiker probe method. In short chains of up to ten units, we observe the crossover between coherent (tunneling, ballistic) motion and thermally-assisted conduction, with thermal effects enhancing the current beyond the quantum coherent limit. We further show that unconventional (nonmonotonic with size) transport behavior emerges when monomer-to-monomer electronic coupling is made large. In long chains, we identify a different behavior, with thermal effects suppressing the conductance below the coherent-ballistic limit. With the goal to identify a minimal model for molecular chains displaying unconventional and effective long-range transport, we simulate a modular polymer with alternating regions of high and low rigidity. Simulations show that, surprisingly, while charge correlations are significantly affected by structuring environmental conditions, reflecting charge delocalization, the electrical resistance displays an averaging effect, and it is not sensitive to this patterning. We conclude by arguing that efficient long-range charge transport requires engineering both internal electronic parameters and environmental conditions.

Quantum Flicker Noise in Atomic and Molecular Junctions.

We report on a quantum form of electronic flicker noise in nanoscale conductors that contains valuable information on quantum transport. This noise is experimentally identified in atomic and molecular junctions and theoretically analyzed by considering quantum interference due to fluctuating scatterers. Using conductance, shot-noise, and flicker-noise measurements, we show that the revealed quantum flicker noise uniquely depends on the distribution of transmission channels, a key characteristic of quantum conductors. This dependence opens the door for the application of flicker noise as a diagnostic probe for fundamental properties of quantum conductors and many-body quantum effects, a role that up to now has been performed by the experimentally less-accessible shot noise.

Quantum thermal transport beyond second order with the reaction coordinate mapping.

Standard quantum master equation techniques, such as the Redfield or Lindblad equations, are perturbative to second order in the microscopic system-reservoir coupling parameter λ. As a result, the characteristics of dissipative systems, which are beyond second order in λ, are not captured by such tools. Moreover, if the leading order in the studied effect is higher-than-quadratic in λ, a second-order description fundamentally fails even at weak coupling. Here, using the reaction coordinate (RC) quantum master equation framework, we are able to investigate and classify higher-than-second-order transport mechanisms. This technique, which relies on the redefinition of the system-environment boundary, allows for the effects of system-bath coupling to be included to high orders. We study steady-state heat current beyond second-order in two models: The generalized spin-boson model with non-commuting system-bath operators and a three-level ladder system. In the latter model, heat enters in one transition and is extracted from a different one. Crucially, we identify two transport pathways: (i) System's current, where heat conduction is mediated by transitions in the system, with the heat current scaling as jq ∝ λ2 to the lowest order in λ. (ii) Inter-bath current, with the thermal baths directly exchanging energy between them, facilitated by the bridging quantum system. To the lowest order in λ, this current scales as jq ∝ λ4. These mechanisms are uncovered and examined using numerical and analytical tools. We contend that the RC mapping brings, already at the level of the mapped Hamiltonian, much insight into transport characteristics.

Strong system-bath coupling effects in quantum absorption refrigerators.

We study the performance of three-level quantum absorption refrigerators, paradigmatic autonomous quantum thermal machines, and reveal central impacts of strong couplings between the working system and the thermal baths. Using the reaction coordinate quantum master equation method, which treats system-bath interactions beyond weak coupling, we demonstrate that in a broad range of parameters the cooling window at strong coupling can be captured by a weak-coupling theory, albeit with parameters renormalized by the system-bath coupling energy. As a result, at strong system-bath couplings the window of cooling is significantly reshaped compared to predictions of weak-coupling treatments. We further show that strong coupling admits direct transport pathways between the thermal reservoirs. Such beyond-second-order transport mechanisms are typically detrimental to the performance of quantum thermal machines. Our study reveals that it is inadequate to claim for either a suppression or an enhancement of the cooling performance as one increases system-bath coupling-when analyzed against a single parameter and in a limited domain. Rather, a comprehensive approach should be adopted so as to uncover the reshaping of the operational window.

Periodically Driven Quantum Thermal Machines from Warming up to Limit Cycle.

Theoretical treatments of periodically driven quantum thermal machines (PD-QTMs) are largely focused on the limit-cycle stage of operation characterized by a periodic state of the system. Yet, this regime is not immediately accessible for experimental verification. Here, we present a general thermodynamic framework that handles the performance of PD-QTMs both before and during the limit-cycle stage of operation. It is achieved by observing that periodicity may break down at the ensemble average level, even in the limit-cycle phase. With this observation, and using conventional thermodynamic expressions for work and heat, we find that a complete description of the first law of thermodynamics for PD-QTMs requires a new contribution, which vanishes only in the limit-cycle phase under rather weak system-bath couplings. Significantly, this contribution is substantial at strong couplings even at limit cycle, thus largely affecting the behavior of the thermodynamic efficiency. We demonstrate our framework by simulating a quantum Otto engine building upon a driven resonant level model. Our results provide new insights towards a complete description of PD-QTMs, from turn-on to the limit-cycle stage and, particularly, shed light on the development of quantum thermodynamics at strong coupling.

Universal Bounds on Fluctuations in Continuous Thermal Machines.

We study bounds on ratios of fluctuations in steady-state time-reversal energy conversion devices. In the linear response regime, we prove that the relative fluctuations (precision) of the output current (power) is always lower bounded by the relative fluctuations of the input current (heat current absorbed from the hot bath). As a consequence, the ratio between the fluctuations of the output and input currents are bounded both from above and below, where the lower (upper) bound is determined by the square of the averaged efficiency (square of the Carnot efficiency) of the engine. The saturation of the lower bound is achieved in the tight-coupling limit when the determinant of the Onsager response matrix vanishes. Our analysis can be applied to different operational regimes, including engines, refrigerators, and heat pumps. We illustrate our findings in two types of continuous engines: two-terminal coherent thermoelectric junctions and three-terminal quantum absorption refrigerators. Numerical simulations in the far-from-equilibrium regime suggest that these bounds apply more broadly, beyond linear response.

Harmonic chains and the thermal diode effect.

Harmonic oscillator chains connecting two harmonic reservoirs at different constant temperatures cannot act as thermal diodes, irrespective of structural asymmetry. However, here we prove that perfectly harmonic junctions can rectify heat once the reservoirs (described by white Langevin noise) are placed under temperature gradients, which are asymmetric at the two sides, an effect that we term "temperature-gradient harmonic oscillator diodes." This nonlinear diode effect results from the additional constraint-the imposed thermal gradient at the boundaries. We demonstrate the rectification behavior based on the exact analytical formulation of steady-state heat transport in harmonic systems coupled to Langevin baths, which can describe quantum and classical transport, both regimes realizing the diode effect under the involved boundary conditions. Our study shows that asymmetric harmonic systems, such as room-temperature hydrocarbon molecules with varying side groups and end groups, or a linear lattice of trapped ions may rectify heat by going beyond simple boundary conditions.

Coherences and the thermodynamic uncertainty relation: Insights from quantum absorption refrigerators.

The thermodynamic uncertainty relation, originally derived for classical Markov-jump processes, provides a tradeoff relation between precision and dissipation, deepening our understanding of the performance of quantum thermal machines. Here, we examine the interplay of quantum system coherences and heat current fluctuations on the validity of the thermodynamics uncertainty relation in the quantum regime. To achieve the current statistics, we perform a full counting statistics simulation of the Redfield quantum master equation. We focus on steady-state quantum absorption refrigerators where nonzero coherence between eigenstates can either suppress or enhance the cooling power, compared with the incoherent limit. In either scenario, we find enhanced relative noise of the cooling power (standard deviation of the power over the mean) in the presence of system coherence, thereby corroborating the thermodynamic uncertainty relation. Our results indicate that fluctuations necessitate consideration when assessing the performance of quantum coherent thermal machines.

Hamiltonian transformability, fast adiabatic dynamics and hidden adiabaticity.

We prove the existence of a unitary transformation that enables two arbitrarily given Hamiltonians in the same Hilbert space to be transformed into one another. The result is straightforward yet, for example, it lays the foundation to implementing or mimicking dynamics with the most controllable Hamiltonian. As a promising application, this existence theorem allows for a rapidly evolving realization of adiabatic quantum computation by transforming a Hamiltonian where dynamics is in the adiabatic regime into a rapidly evolving one. We illustrate the theorem with examples.

On the definitions and simulations of vibrational heat transport in nanojunctions.

Thermal transport through nanosystems is central to numerous processes in chemistry, material sciences, and electrical and mechanical engineering, with classical molecular dynamics as the key simulation tool. Here, we focus on thermal junctions with a molecule bridging two solids that are maintained at different temperatures. The classical steady state heat current in this system can be simulated in different ways, either at the interfaces with the solids, which are represented by thermostats, or between atoms within the conducting molecule. We show that while the latter, intramolecular definition feasibly converges to the correct limit, the molecule-thermostat interface definition is more challenging to converge to the correct result. The problem with the interface definition is demonstrated by simulating heat transport in harmonic and anharmonic one-dimensional chains illustrating unphysical effects such as thermal rectification in harmonic junctions.

Sharp Negative Differential Resistance from Vibrational Mode Softening in Molecular Junctions.

We unravel the critical role of vibrational mode softening in single-molecule electronic devices at high bias. Our theoretical analysis is carried out with a minimal model for molecular junctions, with mode softening arising due to quadratic electron-vibration couplings, and by developing a mean-field approach. We discover that the negative sign of the quadratic electron-vibration coupling coefficient can realize, at high voltage, a sharp negative differential resistance (NDR) effect with a large peak-to-valley ratio. Calculated current-voltage characteristics, obtained based on physical parameters for a nitro-substituted oligo(phenylene ethynylene) junction, agree very well with the measurements. Our results establish that vibrational mode softening is a crucial effect at high voltage, underlying NDR, a substantial diode effect, and the breakdown of current-carrying molecular junctions.

Thermodynamic uncertainty relation in thermal transport.

We use the fundamental nonequilibrium steady-state fluctuation symmetry and derive a condition on the validity of the thermodynamic uncertainty relation (TUR) in thermal transport problems, classical and quantum alike. We test this condition and study the breakdown of the TUR in different thermal transport junctions of bosonic and electronic degrees of freedom. We prove that the TUR is valid in harmonic oscillator junctions. In contrast, in the nonequilibrium spin-boson model, which realizes many-body effects, it is satisfied in the Markovian limit, but violations arise as we tune (reduce) the cutoff frequency of the thermal baths, thus observing non-Markovian dynamics. We consider heat transport by noninteracting electrons in a tight-binding chain model. We show that the TUR is feasibly violated by tuning, e.g., the hybridization energy of the chain to the metal leads. These results manifest that the validity of the TUR relies on the statistics of the participating carriers, their interaction, and the nature of their couplings to the macroscopic contacts (metal electrodes and phonon baths).