Molecular Transport Junctions Research Articles

Optimal tree tensor network operators for tensor network simulations: Applications to open quantum systems.

Tree tensor network states (TTNS) decompose the system wavefunction to the product of low-rank tensors based on the tree topology, serving as the foundation of the multi-layer multi-configuration time-dependent Hartree method. In this work, we present an algorithm that automatically constructs the optimal and exact tree tensor network operators (TTNO) for any sum-of-product symbolic quantum operator. The construction is based on the minimum vertex cover of a bipartite graph. With the optimal TTNO, we simulate open quantum systems, such as spin relaxation dynamics in the spin-boson model and charge transport in molecular junctions. In these simulations, the environment is treated as discrete modes and its wavefunction is evolved on equal footing with the system. We employ the Cole-Davidson spectral density to model the glassy phonon environment and incorporate temperature effects via thermo-field dynamics. Our results show that the computational cost scales linearly with the number of discretized modes, demonstrating the efficiency of our approach.

Peptide-Based Electrical Array Sensor for Discriminating Heavy Metal Ions.

Charge transport in molecular junctions provides an excellent way to investigate the response of molecules to intrinsic changes and external stimuli, exhibiting powerful potential for developing sensors. However, achieving multianalyte recognition remains a challenge. Herein, we innovatively developed an electrical array sensor based on peptide self-assembled layers for discriminating various heavy metal ions. Three peptide sequences were designed as sensing units with varying binding affinities for different metal ions. Electrical measurements demonstrated that different metal ions diversely affect the charge transport of peptide junctions. By using principal component analysis, a clear discrimination between the five kinds of heavy metal ions can be achieved. In the analysis of real samples, the array sensor showed a reliable anti-interference capability. The array sensor offers possibilities for large-area molecular junctions to construct functional molecular sensing devices.

Cluster Formation of Self-Assembled Triarylbismuthanes and Charge Transport Characterizations of Gold-Triarylbismuthane-Gold Junctions.

Organometallic molecules are promising for molecular electronic devices due to their potential to improve electrical conductance through access to complex orbital covalency that is not available to light-element organic molecules. However, studies of the formation of organometallic monolayers and their charge transport properties are scarce. Here, we report the cluster formation and charge transport properties of gold-triarylbismuthane-gold molecular junctions. We found that triarylbismuthane molecules with -CN anchoring groups form clusters during the creation of self-assembled submonolayers. This clustering is attributed to strong interactions between the bismuth (Bi) center and the nitrogen atom in the -CN group of adjacent molecules. Examination of the influence of -NH2 and -CN anchoring groups on junction conductance revealed that, despite a stronger binding energy between the -NH2 group and gold, the conductance per molecular unit (i.e., molecule for the -NH2 group and cluster for the -CN group) is higher with the -CN anchoring group. Further analysis showed that an increase in the number of -CN groups from one to three within the junctions leads to a decrease in conductance while increasing the size of the cluster. This demonstrates the significant effects of different anchoring groups and the impact of varying the number of -CN groups on both the charge transport and cluster formation. This study highlights the importance of selecting the appropriate anchoring group in the design of molecular junctions. Additionally, controlling the size and formation of clusters can be a strategic approach to engineering charge transport in molecular junctions.

Marcus Theory and Long-Range Activationless Transport in Molecular Junctions.

Intrachain transport in molecular junctions (MJs) longer than 5 nm has been modeled within the theoretical framework of Marcus theory. We show that in oligo(bisthienylbenzene)-based MJs, electronic transport involves polarons, localized on three monomers that are close to 4 nm in length. They hop and tunnel between adjacent localized sites with reorganization energies λ close to 400-600 meV and electronic coupling parameters Hab close to λ/2. As a consequence, the activation energy for intrachain transport, given by the equation ΔG* = (λ/4)(1 - 2Hab/λ)2, is close to zero, and transport along the chain is activationless, in agreement with experimental observation. On the contrary, similar calculations on conjugated oligonaphthalenefluoreneimine wires show that Hab is much less than λ/2 and predict that the activation energies for intrachain hopping between adjacent sites, close to λ/4, are ∼115 meV. This work proposes a new perspective for understanding long-range activationless transport in MJs beyond the tunneling regime.

Intra-strand phosphate-mediated pathways in microsolvated double-stranded DNA

We argue that dry DNA charge transport in molecular junctions, over distances of tens of nanometers, can take place via independent intra-strand pathways involving the phosphate groups. Such pathways explain recent single-molecule experiments that compare currents in intact and nicked 100 base-pair double-stranded DNA. We explore the conditions that favor independent intra-strand transport channels with the participation of the phosphate groups, as opposed to purely base-mediated transport involving the pi-stacked bases and inter-strand transitions. Our computations demonstrate how long-distance transport pathways in DNA are tuned by the degree of solvation, which affects the level of dynamic disorder in the pi-stacking, and the energies of phosphate-group molecular orbitals.

From Liouville to Landauer: Electron transport and the bath assumptions made along the way

A generalized quantum master equation approach is introduced to describe electron transfer in molecular junctions that spans both the off-resonant (tunneling) and resonant (hopping) transport regimes. The model builds on prior insights from scattering theory but is not limited to a certain parameter range with regard to the strength of the molecule–electrode coupling. The framework is used to study the simplest case of energy and charge transfer between the molecule and the electrodes for a single site noninteracting Anderson model in the limit of symmetric and asymmetric coupling between the molecule and the electrodes. In the limit of elastic transport, the Landauer result is recovered for the current by invoking a single active electron Ansatz and a binary collision approximation for the memory kernel. Inelastic transport is considered by allowing the excitation of electron–hole pairs in the electrodes in tandem with charge transport. In the case of low bias voltages where the Fermi levels of the electrodes remain below the molecular state, it is shown that the current arises from tunneling and the molecule remains neutral. However, once the threshold is reached for aligning the fermi level of one electrode with the molecular orbital, a small amount of charge transfer occurs with a negligible amount of hopping current. While inelasticity in the current has a minimal impact on the shape of the current–voltage curve in the case of symmetric electrode coupling, the results for a slight asymmetry in coupling demonstrate complete charge transfer and a significant drop in current. These results provide encouraging confirmation that the framework can describe charge transport across a wide range of electrode–molecule coupling and provide a unique perspective for developing new master equation treatments for energy and charge transport in molecular junctions. An extension of this work to account for inelastic scattering from electron–vibrational coupling at the molecule is straightforward and will be the subject of subsequent work.

Many-body Effects on Electronic Transport in Molecular Junctions: A Quantum Perspective.

This concept delves into quantum particle transport at the nanoscale, with a particular focus on how electrons move through molecular circuits. The thriving field of single molecular electronics benefits from the unique electrical and other properties of nanostructures. It concentrates on single molecular junctions that serve as bridges between electrodes. In this context, the electronic correlation-induced many-body effect gives rise to resonant states. These states, along with conductance, depend on electron spin. Thus, the field acts as a bridge between quantum and macroscopic worlds, unveiling unique behaviors of electrons. Additionally, external factors, such as magnetic fields and voltages, offer means to control the electron correlation in these junctions.

Determining Transmission Characteristics from Shot-Noise-Driven Electroluminescence in Single-Molecule Junctions.

Biased metal-molecule-metal junctions emit light through electroluminescence, a phenomenon at the intersection of molecular electronics and nanoplasmonics. This can occur when the junction plasmon mode is excited by inelastic electron current fluctuations. Here, we simultaneously measure the conductance and electroluminescence intensity from single-molecule junctions with time resolution in a solution environment at room temperature. We use current versus bias data to determine the molecular junction transport parameters and then relate these to the expected current shot noise. We find that the electroluminescence signal accurately matches the theoretical prediction of shot-noise-driven emission in a large fraction of the molecular junctions studied. This introduces a novel experimental method for qualitatively estimating finite-frequency shot noise in single-molecule junctions under ambient conditions. We further demonstrate that electroluminescence can be used to obtain the level alignment of the frontier orbital dominating transport in the molecular junction.

How substituents tune quantum interference in meta-OPE3 molecular junctions to control thermoelectric transport.

Quantum interference (QI) can strongly affect electric and thermoelectric properties of molecular junctions (MJs). So far, however, a limited number of experimental studies have explored the influence of QI on thermoelectric transport in MJs. To address this open point, we synthesized derivatives of meta-OPE3 with an electron-withdrawing nitro (-NO2) substituent or an electron-donating N,N-dimethyl amine (-NMe2) substituent, attached at two different positions of the central phenylene ring, and systematically studied the electrical conductance and thermopower of the corresponding gold-molecule-gold junctions. We show that (i) the electrical conductance of MJs depends weakly on the polarity of the substituents but strongly on the substitution position and (ii) MJs with the N,N-dimethyl amine group feature a higher thermopower than MJs with the nitro group. We also present calculations based on first principles, which explain these trends and show that the transport properties are highly sensitive to microscopic details in junctions, exhibiting destructive QI features.

Time-Dependent Density Matrix Renormalization Group Method for Quantum Transport with Phonon Coupling in Molecular Junction.

Quantum transport in molecular junctions has attracted great attention. The charge motion in a molecular junction can cause geometric deformation, leading to strong electron phonon coupling, which was often overlooked. We have formulated a nearly exact method to assess the time-dependent current and occupation number in the molecular junction modeled by the electron-phonon coupled bridge state using the time-dependent density matrix renormalization group (TD-DMRG) method. The oscillation period and amplitude of the current are found to be dependent on the electron phonon coupling strength and energy level alignment with the electrodes. In an attempt to better understand these phenomena, we have devised a new approximation that explains the bistability phenomenon and the behavior of steady currents in the strong electron-phonon coupling regime. Comparisons have been made with the multilayer-multiconfiguration time-dependent Hartree (ML-MCTDH) method and the analytical result in the purely electronic limit. Furthermore, we explore the entropy of different orderings, extending to the electron phonon model problems. Regarding finite temperature, the thermal Bogoliubov transformation of both fermions and bosons is used and compared with imaginary time evolution results.

Control over Molecular Orbital Gating and Marcus Inverted Charge Transport in Molecular Junctions with Conjugated Molecular Wires (Adv. Electron. Mater. 2/2023)

Marcus Inverted Region In article number 2200637, Christian A. Nijhuis, Damien Thompson, Enrique Del Barco, and co-workers demonstrate that the mechanism of charge transport can be deliberately switched between the normal and Marcus Inverted regions by controlling the molecule–electrode coupling strength in a series of molecules. The cover shows two almost identical junctions. The only difference is one CH2 which lowers molecule-electrode coupling strength pushing the junctions from direct coherent tunnelling to hopping in the Marcus Inverted region. This ability can improve the energy efficiency of molecular devices. Image credit: Niels van der Velde.

Resonant transport in a highly conducting single molecular junction via metal-metal covalent bond.

Achieving highly transmitting molecular junctions through resonant transport at low bias is key to the next-generation low-power molecular devices. Although resonant transport in molecular junctions was observed by connecting a molecule between the metal electrodes via chemical anchors by applying a high source-drain bias (>1 V), the conductance was limited to <0.1G0, G0 being the quantum of conductance. Herein, we report electronic transport measurements by directly connecting a ferrocene molecule between Au electrodes under ambient conditions in a mechanically controllable break junction setup (MCBJ), revealing a conductance peak at ∼0.2G0 in the conductance histogram. A similar experiment was repeated for ferrocene terminated with amine (-NH2) and cyano (-CN) anchors, where conductance histograms exhibit an extended low conductance feature, including the sharp high conductance peak, similar to pristine ferrocene. The statistical analysis of the data and density functional theory-based transport calculation suggest a possible molecular conformation with a strong hybridization between the Au electrodes, and that the Fe atom of ferrocene is responsible for a near-perfect transmission in the vicinity of the Fermi energy, leading to the resonant transport at a small applied bias (<0.5 V). Moreover, calculations including van der Waals/dispersion corrections reveal a covalent-like organometallic bonding between Au and the central Fe atom of ferrocene, having bond energies of ∼660 meV. Overall, our study not only demonstrates the realization of an air-stable highly transmitting molecular junction, but also provides important insights about the nature of chemical bonding at the metal/organo-metallic interface.

Computational demonstration of isomer- and spin-state-dependent charge transport in molecular junctions composed of charge-neutral iron(II) spin-crossover complexes.

Chemistry offers a multitude of opportunities towards harnessing functional molecular materials with application propensity. One emerging area of interest is molecular spintronics, in which charge and spin degrees of freedom have been used to achieve power-efficient device architectures. Herein, we show that, with the aid of state-of-the-art quantum chemical calculations on designer molecular junctions, the conductance and spin filtering capabilities are molecular structure-dependent. As inferred from the calculations, structural control over the transport can be achieved by changing the position of the thiomethyl (SMe) anchoring groups for Au(111) electrodes in a set of isomeric 2,2'-bipyridine-based metal coordinating ligand entities L1 and L2. The computational studies on heteroleptic iron(II) coordination complexes (1 and 2) composed of L1 and L2 reveal that switching the spin-state of the iron(II) centers, from the low-spin (LS) to high-spin (HS) state, by means of an external electric field stimulus, could, in theory, be performed. Such switching, known as spin-crossover (SCO), renders charge transport through single-molecule junctions of 1 and 2 spin-state-dependent, and the HS junctions are more conductive than the LS junctions for both complexes. Additionally, the LS and HS junctions based on complex 1 are more conductive than those featuring complex 2. Moreover, it is predicted that the spin filtering efficiency (SFE) of the HS junctions strongly depends on the bridging complex geometry, with 1 showing a voltage-dependent SFE, whereas 2 exhibits an SFE of practically 100% over all the studied voltage range. To be pragmatic towards applications, the ligands L1 and L2 and complex 1 have been successfully synthesized, and the spin-state switching propensity of 1 in the bulk state has been elucidated. The results shown in this study might lead to the synthesis and characterization of isomeric SCO complexes with tuneable spin-state switching and charge transport properties.

Control over Molecular Orbital Gating and Marcus Inverted Charge Transport in Molecular Junctions with Conjugated Molecular Wires

AbstractRecently it is discovered that molecular junctions can be pushed into the Marcus Inverted region of charge transport, but it is unclear which factors are important. This paper shows that the mechanism of charge transport across molecular wires can be switched between the normal and Marcus Inverted regions by fine‐tuning the molecule–electrode coupling strength and the tunneling distance across oligophenylene ethynylene (OPE) wire terminated with ferrocene (Fc) abbreviated as S‐OPEnFc (n = 1–3). Coherent tunneling dominates the mechanism of charge transport in junctions with short molecules (n = 1), but for n = 2 or 3 redox reactions become important. By weakening the molecule—electrode interaction by interrupted conjugation, S‐CH2‐OPEnFc, intramolecular orbital gating can occur pushing the junctions completely into the Marcus Inverted region. These results indicated that weak molecule—electrode coupling is important to push junctions into the Marcus Inverted Region.

Key advances in electrochemically-addressable single-molecule electronics

We discuss here recent advancements in the field of electrochemically-gated single-molecule conductance measurements. Important practical techniques and considerations are discussed alongside methods to determine the mechanism of charge transport in molecular junctions. Organic and organometallic systems are discussed, with a focus on systems showing clear electrochemically-gated activity. We highlight a clear need in the field for more in-depth analysis, at higher potential resolution and over a wider electrochemical window to provide more mechanistic insights in such systems. Detailed analyses are key to a deeper understanding of the physical processes operative in single-molecule junctions, and to translate fundamental studies into functional devices.

Hopping or Tunneling? Tailoring the Electron Transport Mechanisms through Hydrogen Bonding Geometry in the Boron-Doped Diamond Molecular Junctions.

Mechanisms of charge transport in molecular junctions involving hydrogen bonds are complex and remain mostly unclear. This study is focused on the elucidation of the electron transfer in a molecular device consisting of two boron-doped diamond interfaces bound with an aromatic linker and a hydrogen bonding surrogating molecule. The projected local density of states (PLODS) analysis coupled with transmission spectra and current–voltage (I–V) simulations show that hydrogen bonding through electron-donating hydroxyl groups in the aromatic linker facilitates electron transfer, while the electron-withdrawing carboxyl group inhibits electron transfer across the junction. Moreover, slight variations in the geometry of hydrogen bonding lead to significant changes in the alignment of the energy levels and positions of the transmission modes. As a result, we observe the switching of the electron transport mechanism from tunneling to hopping accompanied by a change in the shape of the I–V curves and current magnitudes. These results give important information on the tailoring of the electronic properties of molecular junctions.

A DFT Study on the Relationship Between Molecular Structure and Electron Transport in Molecular Junctions

A DFT Study on the Relationship Between Molecular Structure and Electron Transport in Molecular Junctions

Charge transport in molecular junctions: General physical pictures, electrical measurement techniques, and their challenges

AbstractInvestigations on charge transport (CT) at a molecular scale are essential for both fundamental science and miniaturized electronic devices. A prototypical platform for studying CT through molecules is configured as electrode‐molecule‐electrode (EME). The quantum mechanical nature and microscopic interfacial interaction enrich the journey of the transporting charge through EME junctions, which have inspired many theoretical efforts into this interdisciplinary topic. In parallel, several experimental techniques have been developed to characterize EME CT properties. This mini‐review aims to provide general physical pictures for those new to this field to comprehend molecular‐scale CT. Prevalent experimental techniques termed break‐junctions are briefly reviewed, which are often corroborated with simple physical models to characterize CT through EME junctions. Challenges of these techniques and concerns over the use of simple models are also complied herein to facilitate the understanding of CT through various EME systems.

Study of the transport properties of cobalt atomic contact under mechanical strain in a nitrogen atmosphere

Achieving an efficient spin-filter effect and large magneto-resistance in molecular junctions is very important in spintronics. By employing the non-equilibrium Green's function formalism combined with the density functional theory, this study investigated the atomic structures and spin-resolved transport properties of molecular junctions consisting of nitrogen (N2) sandwiched between two cobalt (Co) electrodes with different crystal lattices as a function of stretching distance. In the case of face-centred cubic Co electrodes, our calculations showed that the transport properties depend strongly on the stretching process, which changes the contact between the N2 and Co electrodes. Specifically, the maximum spin polarization is due to the configuration of N2 molecules sitting in parallel with the protruding Co atoms. Furthermore, the Co dxz,yz orbitals interact with the N px,y orbitals, which contribute to the high transmission coefficient at the Fermi level for spin-down electrons. Meanwhile, the Co s-dz2 hybridization orbitals, which interact weakly with the N p orbitals, contribute to the small transmission coefficient at the Fermi level. This can also be verified by the molecular junction model adopting simple monatomic Co chain electrodes, which also show a perfect spin-filter effect and achieve an ideal magnetoresistance. In contrast, in the case of hexagonal Co electrodes, the spin-filter effect disappears. However, the effect appears again by adding one more Co atom to the central point contact. Our findings show that the spin-resolved electronic transport of molecular junctions depends on the stretching process and the nature of the electrodes, which can help in the future design of molecular devices based on the spin degree of freedom.

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.