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Structural breaks occur in timeseries data across a broad range of fields, from economics to nanosciences. For measurements of single-molecule break junctions, structural breaks in conductance versus displacement data occur when the molecular junction ruptures. This moment is significant because the molecule is likely in its most extended geometry, and therefore resembles most closely the geometry used in theoretical predictions. Conventional single-molecule break junction data analysis, on the other hand, typically uses the entire molecular plateau to estimate the single-molecule conductance, which skews the estimate when the plateau is sloped. Borrowing from econometrics, where the study of structural breaks is well established, we present change point detection (CPD) as a tool to search for junction rupture in single-molecule break junction data, and improve estimates in single-molecule conductance. We demonstrate that using CPD instead of the conventional 1D conductance histogram to determine the mean molecular conductance yields a standard deviation in the estimate of typically half that of the conventional approach, greatly improving accuracy. We apply CPD to three separate data sets, two on 4,4'-bipyridine and one on a silane, two at room temperature and one at 4 K, two in one lab, one in another, to show the wide applicability of even the simplest of CPD algorithms: the Chow test. This versatility and better accuracy will propagate into more accurate theoretical simulations. These improved metrics, in turn, will further improve any downstream analyses, including all emerging machine learning approaches., Comment: 33 pages and 11 figures and supporting material of 8 pages and 3 figures

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 experiment. All molecular junctions display transport characteristics consistent with coherent transport and a Fermi alignment approximately in the middle of the HOMO/LUMO 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 the 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 behaviour 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 conductor are required for thermoelectric current generation.

We report a method using scanning tunnelling microscope single molecular break junction to simultaneously measure and correlate the single-molecule thermopower and electrical conductance. In contrast to previously reported approaches, it does not require custom-built electronics and takes advantage of a trace-by-trace calibration of the thermal offset at the Au/Au contact, thus greatly facilitating thermoelectric measurements at the single-molecule level. We report measurements of three molecules: 1,4-di(4-(ethynyl(phenylthioacetate)) benzene, 1,8-octanedithiol, and 4,4'-bipyridine, and determine single-molecule Seebeck coefficients of 12(3), 5(2), and -5(2) microV K-1, respectively. Furthermore, the method statistically correlates the Seebeck voltage offset, electrical conductance, and stretching displacement of the single-molecule junction, and allows for direct comparison with current-distance spectroscopy results obtained at constant bias., Comment: 32 pages, 11 figures including supporting information

The realization of self-assembled molecular-electronic films, whose room-temperature transport properties are controlled by quantum interference (QI), is an essential step in the scale-up QI effects from single molecules to parallel arrays of molecules. Recently, the effect of destructive QI (DQI) on the electrical conductance of self-assembled monolayers (SAMs) has been investigated. Here, through a combined experimental and theoretical investigation, we demonstrate chemical control of different forms of constructive QI (CQI) in cross-plane transport through SAMs and assess its influence on cross-plane thermoelectricity in SAMs. It is known that the electrical conductance of single molecules can be controlled in a deterministic manner, by chemically varying their connectivity to external electrodes. Here, by employing synthetic methodologies to vary the connectivity of terminal anchor groups around aromatic anthracene cores, and by forming SAMs of the resulting molecules, we clearly demonstrate that this signature of CQI can be translated into SAM-on-gold molecular films. We show that the conductance of vertical molecular junctions formed from anthracene-based molecules with two different connectivities differ by a factor of approximately 16, in agreement with theoretical predictions for their conductance ratio based on constructive QI effects within the core. We also demonstrate that for molecules with thiol anchor groups, the Seebeck coefficient of such films is connectivity dependent and with an appropriate choice of connectivity can be boosted by ~50%. This demonstration of QI and its influence on thermoelectricity in SAMs represents a critical step towards functional ultra-thin-film devices for future thermoelectric and molecular-scale electronics applications.

With automated measurements, large data sets can be assembled with relative ease. Often these data sets have a large degree of variance. Nonetheless, we hope to find groups within the data set with shared distinguishing characteristics. Recently Albrecht, et al demonstrated a multi-parameter vector-based classification analysis which provided a powerful means to find clusters within a data set of conductance versus displacement traces measured from single molecular break junctions (Lemmer, et al, Nature Communications, 2016, 7, 12922). An idealized blank tunneling trace was used as a reference to calculate three vector variables. The authors suggested a more appropriate reference can be chosen to better form clusters in the data. Here we propose using a principal component of the correlation matrix calculated from the data set to construct a fast and strategic reference trace. Principal components form an orthogonal basis set in units of the independent variables comprising the correlation matrix. The first principal component, the one corresponding to the largest eigenvalue of the correlation matrix, points in the direction of largest variance in the data. We used both a blank tunneling reference trace and a reference trace constructed from the first principal component of the correlation matrix to analyze a set of 4,4'-bipyridine single molecular break junctions. The blank tunneling reference trace produced a single elongated cluster in the vector analysis plot whereas the reference trace constructed from the principal component distinguished two arms in the cluster. We hypothesize that these two arms are due to groups of traces with either long or short molecular plateaus. Statistically based sorting algorithms, like vector-based categorization techniques, provide an objective framework to formulate such hypothesis and aid in designing new and pointed studies to verify them., Comment: 4 pages, 2 figures