Configuration transitions of individual molecules and atoms on surfaces are traditionally described with energy barriers and attempt rates using an Arrhenius law. This approach yields consistent energy barrier values, but also attempt rates orders of magnitude below expected oscillation frequencies of particles in the meta-stable state. Moreover, even for identical systems, the measurements can yield values differing from each other by orders of magnitude. Using low temperature scanning tunnelling microscopy (STM) to measure an individual dibutyl-sulfide molecule (DBS) on Au(111), we show that we can avoid these apparent inconsistencies if we account for the relative position of tip apex and molecule with accuracy of a fraction of the molecule size. Altering the tip position on that scale modifies the transition's barrier and attempt rate in a highly correlated fashion, which on account of the relation between the latter and entropy results in a single-molecular enthalpy-entropy compensation. By appropriately positioning the tip apex the STM tip can be used to select the operating point on the compensation line and modify the transition rates. The results highlight the need to consider entropy in transition rates of a single molecule, even at temperatures where entropy effects are usually neglected.
A key step towards building single molecule machines is to control the rotation of molecules and nanostructures step by step on a surface. Here, we used the tunneling electrons coming from the tip of a scanning tunneling microscope to achieve the controlled directed rotation of complex o-MeO-DMBI molecules. We studied the adsorption of single o-MeO-DMBI molecules on Au(111) by scanning tunneling microscopy at low temperature. The enantiomeric form of the molecule on the surface can be determined by imaging the molecule by STM at high bias voltage. We observed by lateral manipulation experiment…
Single molecules are nanoscale thermodynamic systems with few degrees of freedom. Thus, the knowledge of their entropy can reveal the presence of microscopic electron transfer dynamics, that are difficult to observe otherwise. Here, we apply thermocurrent spectroscopy to directly measure the entropy of a single free radical molecule in a magnetic field. Our results allow us to uncover the presence of a singlet to triplet transition in one of the redox states of the molecule, not detected by conventional charge transport measurements. This highlights the power of thermoelectric measurements whi…
We investigate gold-4,4'-bipyridine-gold single-molecule junctions with the mechanically controllable break junction technique at cryogenic temperature ($T=4.2\,\text{K}$). We observe bistable probabilistic conductance switching between the two molecular binding configurations, influenced both by the mechanical actuation, and the applied voltage. We demonstrate that the relative dominance of the two conductance states is tunable by the electrode displacement, whereas the voltage manipulation induces an exponential speedup of both switching times. The detailed investigation of the voltage-tunab…
A condensed matter platform for analogue simulation of complex two-dimensional molecular bonding configurations, based on optically trapped exciton-polariton condensates is proposed. The stable occupation of polariton condensates in the excited states of their optically configurable potential traps permits emulation of excited atomic orbitals. A classical mean field model describing the dissipative coupling mechanism between p-orbital condensates is derived, identifying lowest threshold condensation solutions as a function of trap parameters corresponding to bound and antibound $π$ and $σ$ bon…
Quantum interference can profoundly affect charge transport in single molecules, but experiments can usually measure only the conductance at the Fermi energy. Because in general the most pronounced features of the quantum interference are not located at the Fermi energy, it is highly desirable to probe charge transport in a broader energy range. Here by the method of electrochemical gating, we measure the conductance and map the transmission functions of single molecules at and around the Fermi energy, and study signatures associated with constructive and destructive interference. With the ele…
Quantum-interference-controlled three-terminal molecular transistors based on a single ring-shaped-molecule connected to graphene nanoribbon electrodes
We discuss implications of a recent experimental breakthrough which uses a fluorescence-doped flexible semiconducting polymer to construct a single-molecule sensor which can detect ultra-weak forces in the molecular environment, with a grey scale down to 300 femtonewtons.
Density of States Proportion on Charge Transfer Kinetics in Breathing Fermionic Systems of Molecules and Materials: A Perspective of Entropy-Ruled Method
We report results of theoretical studies of thermoelectric efficiency of single-molecule junctions with long molecular linkers. The linker is simulated by a chain of identical sites described using a tight-binding model. It is shown that thermoelectric figure of merit ZT strongly depends on the bridge length, being controlled by the lineshape of electron transmission function within the tunnel energy range corresponding to HOMO/LUMO transport channel. Using the adopted model we demonstrate that ZT may significantly increase as the linker lengthens, and that gateway states on the bridge (if any…
In this article, we address fluorescence of single molecule inside a plasmonic picocavity by proposing a semi-classical theory via combining the macroscopic quantum electrodynamics theory and the open quantum system theory. To gain insights into the experimental results [Nat. Photonics, 14, 693 (2020)], we have further equipped this theory with the classical electromagnetic simulation of the pico-cavity, formed by single atom decorated silver STM tip and a silver substrate, and the time-dependent density functional theory calculation of zinc phthalocyanine molecule. Our simulations not only re…
We report the direct observation of quantum coupling in individual quantum dot molecules and its manipulation using static electric fields. A pronounced anti-crossing of different excitonic transitions is observed as the electric field is tuned. Comparison of our experimental results with theory shows that the observed anti-crossing occurs between excitons with predominant spatially \emph{direct} and \emph{indirect} character. The electron component of the exciton wavefunction is shown to have molecular character at the anti-crossing and the quantum coupling strength is deduced optically. In a…
The single-molecule conductance of a 3-ring, conjugated azomethine was studied using the mechanically controlled breakjunction technique. Charge transport properties are found to be comparable to vinyl-based analogues; findings are supported with density functional calculations. The simple preparation and good transport properties make azomethine-based molecules an attractive class for use in polymer and single-molecule organic electronics.
We investigate the generation of entanglement through a quantum dot molecule under the influence of vibrational phonon modes in a bias voltage junction. The molecular quantum dot system is realized by coupled quantum dots inside a suspended carbon nanotube. We consider the dynamical entanglement as a function of bias voltage and temperature by taking into account the electron-phonon interaction. In order to generate the robust entanglement between quantum dots and preserve it to reach the maximal achievable amount steadily, we introduce an asymmetric coupling protocol and apply the easy tunabl…
Recent observations of destructive quantum interference in single-molecule junctions confirm the role played by quantum effects in the electronic conductance properties of molecular systems. We show here that the destructive interference can be turned ON or OFF within the same molecular system by mechanically controlling its conformation. Using a combination of ab-initio calculations and single-molecule conductance measurements, we demonstrate the existence of a quasi-periodic destructive quantum interference pattern along the breaking traces of π-π stacked molecular dimers. The detection of t…
Entropy effects substantially modify the growth of self-assembled Ge nanostructures on vicinal Si (001) surfaces. As shown by variable temperature scanning tunneling microscopy, this leads to new types of one dimensional nanostructures that are not only tunable in size and shape but can be fully reversible erased and reformed without changes in final sizes and shapes. This unique behavior is caused by the free surface energy renormalization caused by the large step entropy of vicinal surfaces. In thermodynamic equilibrium, this favors the formation of a planar 2D surface at higher temperatures…
We investigate the influence of vibrational phonon modes on the entanglement through a quantum dot molecule under the bias voltage-driven field. The molecular quantum dot system can be realized by coupled quantum dots in the middle of the suspended carbon nanotube. This system would be described by the Anderson-Holstein model and also can be analyzed by the polaron master equation in Markovian regime. In the presence of electron-phonon interaction, we study the entanglement as a function of bias voltage and temperature. Despite entanglement degradation because of phonon decoherence, we employ …
Thermodynamic probes can be used to deduce microscopic internal dynamics of nanoscale quantum systems. Several direct entropy measurement protocols based on charge transport measurements have been proposed and experimentally applied to single-electron devices. To date, these methods have relied on (quasi-)equilibrium conditions between the nanoscale quantum system and its environment, which constitutes only a small subset of the experimental conditions available. In this paper, we establish a thermodynamic analysis method based on stochastic thermodynamics, that is valid far from equilibrium c…
Controlled Coherent Coupling in a Quantum Dot Molecule Revealed by Ultrafast Four-Wave Mixing Spectroscopy
Wrocław University of Science and Technology（弗罗茨瓦夫科技大学）；School of Physics, Trinity College Dublin（都柏林三一学院物理学院）；Technische Universität Berlin（柏林工业大学）；Ruhr-Universität Bochum（波鸿鲁尔大学）；Wrocław University of Technology（弗罗茨瓦夫理工大学）；Technische Universität München（慕尼黑工业大学）；Universität Paderborn（帕德博恩大学）；Université Grenoble Alpes（格勒诺布尔阿尔卑斯大学）
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…
