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Chemistry of the Au-S interface at the nanoscale is one of the most complex systems to study, as the nature and strength of the Au-S bond change under different experimental conditions. In this study, using mechanically controlled break junction technique, we probed the conductance and analyzed Flicker noise for several aliphatic and aromatic thiol derivatives and thioethers. We demonstrate that Flicker noise can be used to unambiguously differentiate between stronger chemisorption (Au-SR) and weaker physisorption (Au-SRR′) type interactions. The Flicker noise measurements indicate that the gold rearrangement in chemisorbed Au-SR junctions resembles that of the Au rearrangement in pure Au-Au metal contact breaking, which is independent of the molecular backbone structure and the resulting conductance. In contrast, thioethers showed the formation of a weaker physisorbed Au-SRR′ type bond, and the Flicker noise measurement indicates the changes in the Au-anchoring group interface but not the Au-Au rearrangement like that in the Au-SR case. Additionally, by employing single-molecular conductance and Flicker noise analysis, we have probed the interfacial electric field-catalyzed ring-opening reaction of cyclic thioether under mild environmental conditions, which otherwise requires harsh chemical conditions for cleavage of the C-S bond. All of our conductance measurements are complemented by NEGF transport calculations. This study illustrates that the single-molecule conductance, together with the Flicker noise measurements can be used to tune and monitor chemical reactions at the single-molecule level.

We report on the single-molecule electronic and thermoelectric properties of strategically chosen anthracene-based molecules with anchor groups capable of binding to noble metal substrates, such as gold and platinum. Specifically, we study the effect of different anchor groups, as well as quantum interference, on the electric conductance and the thermopower of gold/single-molecule/gold junctions and generally find good agreement between theory and experiments. All molecular junctions display transport characteristics consistent with coherent transport and a Fermi alignment approximately in the middle of the highest occupied molecular orbital/lowest unoccupied molecular orbital gap. Single-molecule results are in agreement with previously reported thin-film data, further supporting the notion that molecular design considerations may be translated from the single- to many-molecule devices. For combinations of anchor groups where one binds significantly more strongly to the electrodes than the other, the stronger anchor group appears to dominate the thermoelectric behavior of the molecular junction. For other combinations, the choice of electrode material can determine the sign and magnitude of the thermopower. This finding has important implications for the design of thermoelectric generator devices, where both n- and p-type conductors are required for thermoelectric current generation.

Dialkynylferrocenes are interesting candidates for molecular electronics. Herein, numerous experiments are applied to probe their properties both as single-molecules and in monolayers, demonstrating unique geometric and thermoelectric properties.

In this tutorial review, we will describe crucial aspects related to the application of machine learning to help users avoid the most common pitfalls. The examples we present will be based on data from the field of molecular electronics, specifically single-molecule electron transport experiments, but the concepts and problems we explore will be sufficiently general for application in other fields with similar data. In the first part of the tutorial review, we will introduce the field of single-molecule transport, and provide an overview of the most common machine learning algorithms employed. In the second part of the tutorial review, we will show, through examples grounded in single-molecule transport, that the promises of machine learning can only be fulfilled by careful application. We will end the tutorial review with a discussion of where we, as a field, could go from here.

Charge transport by tunnelling is one of the most ubiquitous elementary processes in nature. Small structural changes in a molecular junction can lead to significant difference in the single-molecule electronic properties, offering a tremendous opportunity to examine a reaction on the single-molecule scale by monitoring the conductance changes. Here, we explore the potential of the single-molecule break junction technique in the detection of photo-thermal reaction processes of a photochromic dihydroazulene/vinylheptafulvene system. Statistical analysis of the break junction experiments provides a quantitative approach for probing the reaction kinetics and reversibility, including the occurrence of isomerization during the reaction. The product ratios observed when switching the system in the junction does not follow those observed in solution studies (both experiment and theory), suggesting that the junction environment was perturbing the process significantly. This study opens the possibility of using nano-structured environments like molecular junctions to tailor product ratios in chemical reactions.

As the field of unimolecular electronics develops, there is growing interest in the development of functionalised molecular wires, such as switches, which will allow for more complex molecular-scale circuits. To this end, a three redox state single molecule switch, 1, based on bis(pyrrolo)tetrathiafulvalene (BPTTF) has been designed, synthesised and investigated using scanning tunnelling microscopy break junction (STM-BJ) studies and quantum transport calculations. Oxidising the BPTTF unit increases its conjugation, which was anticipated to increase the molecular conductance of 1. By changing the redox state of 1 electrochemically it was possible to vary the single molecule conductance by more than an order of magnitude (from 10-5.2G0 to 10-3.8G0). Simulations afforded a qualitatively similar trend. An additional, higher conductance feature is present in most traces at junction sizes of around 2.0 nm-further extension affords the switchable lower conductance feature at junction sizes closer to the molecular length (ca. 3.0 nm). Analysis of the conductance traces shows that these two conductance features occur sequentially in nearly all junctions. This behaviour is attributed to an alternative initial junction conformation in which one or more of the BPTTF sulfur atoms acts as an anchoring group. This hypothesis is supported by a computational study of binding conformations and STM-BJ studies on a model compound, 2, with only one thiol anchor. Our results indicate that the redox properties of BPTTF make it an excellent candidate for use in single molecule switches.

Joseph M Hamill,1 Kun Wang,1 Bingqian Xu1,21Single Molecule Study Laboratory, College of Engineering and Nanoscale Science and Engineering Center, 2College of Engineering, University of Georgia, Athens, GA, USAAbstract: Mechanically controlled break-junction techniques, which emerged right after the invention of scanning tunneling microscopy, have enabled substantial progress in characterizing single-molecule junctions toward the ultimate goal of molecular devices. Dramatic advances have been made in design, fabrication, control, and understanding of the measurements of single-molecule junctions over the past decade. In this overview, we present the evolution of some of the recent issues, and an outlook for further developments in mechanically controlled break-junction techniques for characterizing molecular junctions. Topics of recent interest include contact geometry, electrochemical redox experiments, external bias effect, and environmental influences. Each will need further investigation to thoroughly understand the experimental information revealed from a molecular junction.Keywords: mechanically controlled molecular break junction, scanning probe microscopy

Force and conductance, measured across 4,4′-bipyridine simultaneously, are crosscorrelated using a two dimensional (2D) histogram method. The result is a 2D multivariate statistical analysis superior to current one dimensional histogram techniques for exploring significant conductance and force modulations within SMBJs. This method is sensitive enough to crosscorrelate signal modulations between force and conductance traces associated with contact geometry perturbations predicted in literature such as Au-molecule contact twisting and slipping during junction elongation.

Experimental study of the charge transport properties associated with structural variations due to a change in the ionic environment will provide essential physical information in determining the nature of DNA molecules. This work reports an experimental study of the change in electronic transport properties induced by the conformational transition of a poly d(GC)4 DNA. By gradually increasing the concentration of MgCl2 in the buffer solution from 0 M to 4 M, the conductance of the single DNA molecule decreased by two orders of magnitude. Circular dichroism (CD) measurements confirmed that a B to Z conformational transition caused the reduction in conductance. Using a stretch-hold mode scanning probe microscopy break junction (SPMBJ) technique, this B-Z transition process was monitored and a transition trend line was successfully achieved from conductance measurements alone. The transition midpoint occurred at a MgCl2 concentration of 0.93 M for this DNA sequence. This method provides a general tool to study transitions of molecular properties associated with conductance differences.