The realization of single-molecule thermal conductance measurements has driven the need for theoretical tools to describe conduction processes that occur over atomistic length scales. In macroscale systems, the principle that is typically used to understand thermal conductivity is Fourier's law. At molecular length scales, however, deviations from Fourier's law are common in part because microscale thermal transport properties typically depend on the complex interplay between multiple heat conduction mechanisms. Here, the thermal transport properties that arise from electron transfer across a thermal gradient in a molecular conduction junction are examined theoretically. We illustrate how transport in a model junction is affected by varying the electronic structure and length of the molecular bridge in the junction as well as the strength of the coupling between the bridge and its surrounding environment. Three findings are of note: First, the transport properties can vary significantly depending on the characteristics of the molecular bridge and its environment; second, the system's thermal conductance commonly deviates from Fourier's law; and third, in properly engineered systems, the magnitude of electron hopping thermal conductance is similar to what has been measured in single-molecule devices.
Recent studies indicated that helical organic molecules, such as DNA and $α$-helical protein, can behave as Thouless quantum pumps when a rotating electric field is applied perpendicularly to their helical axes. Here we investigate the influence of long-range hoppings on this topological pumping of electrons in single-helical organic molecules. Under variation of the long-range hoppings governed by a decay exponent $μ$, we find an energy gap in the molecular band structure closes at a critical value $μ_c$ of the decay exponent and reopens for $μ$ deviating from $μ_c$. The relevant bulk bands i…
For defining the conductance of single molecule junctions with a redox functionality in an electrochemical cell, two conceptually different electron transport mechanisms, namely coherent tunnelling and vibrationally induced hopping compete with each other, where implicit parameters of the setup such as the length of the molecule and the applied gate voltage decide which mechanism is the dominant one. Although coherent tunnelling is most efficiently described within Landauer theory, while the common theoretical treatment of electron hopping is based on Marcus theory, both theories are adequate …
We study the electrical conductance $G$ and the thermopower $S$ of single-molecule junctions, and reveal signatures of different transport mechanisms: off-resonant tunneling, on-resonant coherent (ballistic) motion, and multi-step hopping. These mechanisms are identified by studying the behavior of $G$ and $S$ while varying molecular length and temperature. Based on a simple one-dimensional model for molecular junctions, we derive approximate expressions for the thermopower in these different regimes. Analytical results are compared to numerical simulations, performed using a variant of Büttik…
The transport properties of junctions composed of a central region tunnel-coupled to external electrodes are frequently studied within the single-impurity Anderson model with Hubbard on-site interaction. In the present work, we supplement the model with an important ingredient, namely the charge-bond interaction, also known as correlated or assisted hopping. Correlated hopping enters the second-quantised Hamiltonian, written in the Wannier representation, as an off-diagonal many-body term. Using the equation of motion technique, we study the effect of the correlated hopping on the spectral and…
We investigate transient spin-dependent thermoelectric signatures in a single-molecule magnet under the effect of a time-dependent voltage pulse. We model the system using nonequilibrium Green's functions and a generalized spin equation of motion incorporating the dynamic electronic structure of the molecule. We show that the generated heat current in the system is due to both charge and spin contributions, related to the Peltier and the spin-dependent Peltier effect. There is also a clear signature in the heat current due to the spin dynamics of the single-molecule and a possibility to contro…
A two-site nanostructure (e.g, a "molecule") bridging two conducting leads and connected to a phonon bath is considered. The two relevant levels closest to the Fermi energy are connected each to its lead. The leads have slightly different temperatures and chemical potentials and the nanos- tructure is also coupled to a thermal (third) phonon bath. The 3 x 3 linear transport ("Onsager") matrix is evaluated, along with the ensuing new figure of merit, and found to be very favorable for thermoelectric energy conversion.
The heat capacity C(T) of the interstitial solid solution (CH4)0.4C60 has been investigated in the temperature interval 1.4-120 K. The contribution of CH4 molecules to the heat capacity has been separated. The contributions of CH4 and CD4 molecules to the heat capacity of the solutions (CH4)0.40C60 and (CD4)0.40C60 have been compared. It is found that above 80K the character of the rotational motion of CH4 and CD4 molecules changes from libration to hindered rotation. In the interval 14-35 K the heat capacities of CH4 and CD4 molecules are satisfactorily described by contributions of the trans…
Motivated by recent experiments [Lee et al. Nature 498, 209 (2013)], we present here a detailed theoretical analysis of the Joule heating in current-carrying single-molecule junctions. By combining the Landauer approach for quantum transport with ab initio calculations, we show how the heating in the electrodes of a molecular junction is determined by its electronic structure. In particular, we show that in general the heat is not equally dissipated in both electrodes of the junction and it depends on the bias polarity (or equivalently on the current direction). These heating asymmetries are i…
Using acoustic methods we have measured nonlinear AC conductance in 2D arrays of Ge-in-Si quantum dots. The combination of experimental results and modeling of AC conductance of a dense lattice of localized states leads us to the conclusion that the main mechanism of AC conduction in hopping systems with large localization length is due to the charge transfer within large clusters, while the main mechanism behind its non-Ohmic behavior is charge heating by absorbed power.
We examine the electronic heat transport phenomena in nanoscale junctions composed of organic molecules coupled to two metallic reservoirs of different temperatures. The electronic heat flux and its dynamical noise properties are calculated within the scattering (Landauer) formalism with the transmission probability determined by using non-equilibrium Green's functions (NEGF technique). The method based on Taylor series expansion is used to determine nonlinear corrections to the electronic heat flux and its noise power spectral density with up to the second order terms with respect to the temp…
The transport properties of a metal core/semiconductor shell quantum dot molecule (QDM) embedded in a matrix connected to metallic electrodes are theoretically studied in the framework of Keldysh Green function technique. The effects of the electron plasmon interactions (EPIs) on the tunneling current spectra of QDM are examined. The energy levels of the QDs, intradot and interdot Coulomb interactions, electron interdot hopping strengths, and tunneling rates of QDs are renormalized by the EPIs. The differential conductance spectra show peaks arising from the plasmon assisted tunneling process,…
We explore whether localized surface plasmon polariton modes can transfer heat between molecules placed in the hot spot of a nanoplasmonic cavity through optomechanical interaction with the molecular vibrations. We demonstrate that external driving of the plasmon resonance indeed induces an effective molecule-molecule interaction corresponding to a new heat transfer mechanism, which can even be more effective in cooling the hotter molecule than its heating due to the vibrational pumping by the plasmon. This novel mechanism allows to actively control the rate of heat flow between molecules thro…
The rate of electron transfer between a molecular species and a metal, each at a different local temperature, is examined theoretically through implementation of a bithermal (characterized by two temperatures) Marcus formalism. Expressions for the rate constant and the electronic contribution to a heat transfer mechanism which is induced by the temperature gradient between molecule and metal are constructed. The system of coupled dynamical equations describing the electronic and thermal currents are derived and examined over diverse ranges of reaction geometries and temperature gradients. It i…
We have theoretically studied the thermoelectric properties of serially coupled quantum dots (SCQD) embedded in an insulator matrix connected to metallic electrodes. In the framework of Keldysh Green's function technique, the Landauer formula of transmission factor is obtained by using the equation of motion method. Based on such analytical expressions of charge and heat currents, we calculate the electrical conductance, Seebeck coefficient, electron thermal conductance and figure of merit (ZT) of SCQD in the linear response regime. The effects of electron Coulomb interactions on the reduction…
The transport of electrons through serially coupled quantum dot molecules (SCQDM) is investigated theoretically for application as an energy harvesting engine (EHE), which converts thermal heat to electrical power. We demonstrate that the charge current driven by a temperature bias shows bipolar oscillatory behavior with respect to gate voltage due to the unbalance between electrons and holes, which is different from the charge current driven by an applied bias. In addition, we reveal a Lenz's law between the charge current and the thermal induced voltage. The efficiency of EHE is higher for S…
A universal mechanism for strong magnetic-field effects of nonmagnetic organic semiconductors is presented. A weak magnetic field (less than hundreds mT) can substantially change the charge carrier hopping coefficient between two neighboring organic molecules when the magnetic length is not too much longer than the molecule-molecule separation and localization length of electronic states involved. Under the illumination of lights or under a high electric field, the change of hopping coefficients leads also to the change of polaron density so that photocurrent, photoluminescence, electrolumines…
We discuss nuclear dynamics at molecule-metal interfaces including non-equilibrium molecular junctions. Starting from the many-body states (pseudoparticle) formulation of the molecule-metal system in the molecular vibronic basis, we introduce gradient expansion in order to reduce the adiabatic nuclear dynamics (that is, nuclear dynamics on a single molecular potential surface) into its semi-classical form while maintaining the effect of the non-adiabatic electronic transitions between different molecular charge states. This yields a set of equations for the nuclear dynamics in the presence of …
Thermal radiative phenomena can be strongly influenced by the coupling of phonons and long-range electromagnetic fields at infrared frequencies. Typically employed macroscopic descriptions of thermal fluctuations tend to ignore atomistic effects that become relevant at nanometric scales, whereas purely microscopic treatments ignore long-range, geometry-dependent electromagnetic effects. We describe a mesoscopic framework for modeling thermal fluctuation phenomena among molecules in the vicinity of macroscopic bodies, conjoining atomistic treatments of electronic and vibrational fluctuations ob…
We present a theoretical study of the heat dissipation in single-molecule junctions. In order to investigate the heat dissipation in the electrodes and the relationship between the transmission spectra and the electronic structures, we consider a toy model that in which electrodes linked by a two-level molecular bridge. By using of the Landauer approach, we show how heat dissipation in the electrodes of a molecular junction is related to its transmission characteristics. We show that in general heat is not equally dissipated in the left and right electrodes of the junction and it depends on th…
Thermal transport in solids changes its nature from phonon propagation that suffers from perturbative scattering to thermally activated hops between localized vibrational modes as the level of disorder increases. Models have been proposed to understand these two distinct extremes that predict opposite temperature dependence of the thermal conductivity, but not for the transition or the intermediate regime. Here we explore thermal transport in two-dimensional crystalline and amorphous silica with varying levels of disorder, α, by performing atomistic simulations as well as analysis based on the…
We present a consistent theory of energy balance and conversion in a single-molecule junction with strong interactions between electrons on the molecular linker (dot) and phonons in the nuclear environment where the Marcus-type electron hopping processes predominate in the electron transport. It is shown that the environmental reorganization and relaxation that accompany electron hopping energy exchange between the electrodes and the nuclear (molecular and solvent) environment may bring a moderate local cooling of the latter in biased systems. The effect of a periodically driven dot level on t…
The nonlinear electron and heat currents of quantum dot molecules (QDMs) under a temperature bias are theoretically investigated, including all correlation functions arising from electron Coulomb interactions in QDMs. Unlike the case of double QDs, the maximum efficiency of serially coupled triple QDs (SCTQD) occurs in the orbital depletion regime owing to the interdot Coulomb blockade. The electron current in SCTQD shows a bipolar oscillatory behavior with respect to the variation of QD energy levels, whereas the heat current does not show such a behavior. This is mainly attributed to thermal…
The mechanism of thermal conductivity in amorphous polymers, especially polymer fibers, is unclear in comparison with that in inorganic materials. Here, we report the observation of across over of heat conduction behavior from three dimensions (3D) to quasi-one dimension (1D) in Polyimide(PI) nanofibers at a given temperature. A theoretical model based on the random walk theory has been proposed to quantitatively describe the interplay between the inter-chain hopping and the intra-chain hopping in nanofibers. This model explains well the diameter dependence of thermal conductivity and also spe…
The heat capacity of bundles of closed-cap single-walled carbon nanotubes (SWNT) with one-dimensional chains of nitrogen molecules adsorbed in the grooves has been first experimentally studied at temperatures from 2K to 40K using an adiabatic calorimeter. The contribution of nitrogen C(T) to the total heat capacity has been separated. In the region 2-8K the behaviour of the curve C(T) is qualitatively similar to the theoretical prediction of the phonon heat capacity of 1D chains of krypton (Kr) atoms localized in the grooves of SWNT bundles. Below 3K the dependence C(T) is linear. Above 8K the…
Density of States Proportion on Charge Transfer Kinetics in Breathing Fermionic Systems of Molecules and Materials: A Perspective of Entropy-Ruled Method
With the objective to understand 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 nonequ…
A Flickering Resonance Degeneracy on Entropy-Ruled Charge Transport in the Extended Hopping Sites for Biological Systems: Role of Static-to-Dynamic Disorder Transition
KPR Institute of Engineering and Technology（KPR工程学院与技术学院）
Thermal transport through nanosystems is central to numerous processes in chemistry, material sciences, 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 …
Heat Capacity Anomalies and Thermal Crossovers in Finite Su-Schrieffer-Heeger Chains
Universidade Federal Fluminense（弗鲁米嫩塞联邦大学）；Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México（墨西哥国立自治大学核科学研究所）；Faculty of Electric Engineering, Universidad Michoacana de San Nicolás de Hidalgo（圣尼古拉斯德伊达尔戈米却肯自治大学电气工程学院）；Centro de Ciencias Exactas, Universidad del Bío-Bío（比奥比奥大学精确科学中心）；Departamento de Ciencias Básicas de la Facultad de Ciencias, Universidad del Bío-Bío（比奥比奥大学理学院基础科学系）
Can tunneling current in molecular junctions be so strongly temperature dependent to challenge a hopping mechanism? Analytical formulas answer this question and provide important insight into large area junctions
We show that the simplest of existing molecules -- closed-shell diatomics not interacting with one another -- host topological charges when driven by periodic far-off-resonant laser pulses. A periodically kicked molecular rotor can be mapped onto a ''crystalline'' lattice in angular momentum space. This allows to define quasimomenta and the band structure in the Floquet representation, by analogy with the Bloch waves of solid-state physics. Applying laser pulses spaced by $1/3$ of the molecular rotational period creates a lattice with three atoms per unit cell with staggered hopping. Within th…
