Optical, purely mechanical, and combined opto-mechanical switching cycles of a molecular switch embedded in a metal junction are investigated using density functional theory and (excited state) ab initio molecular dynamics. The nanomechanical simulations are done on realistic models of gold electrode tips bridged by a single dithioazobenzene molecule. Comparison of different tip models shows that the nature of the tips affects switching processes both qualitatively and quantitatively. The study predicts that purely photochemical cis⇌trans switching cycles of suspended azobenzene bridges are mechanically hindered; combined opto-mechanical as well as purely mechanochemical forward and backward switching is, however, feasible.

Most chemical reactions require activation which is conventionally supplied by heat. In stark contrast, mechanical activation by applied external forces opens intriguing novel possibilities. Here, the first direct comparison of mechanical versus thermal activation of bond breaking is provided. Studying both thiolate-copper interfaces and junctions provides evidence for vastly different reaction pathways and product classes. This is understood in terms of directional mechanical manipulation of coordination numbers and system fluctuations in the process of mechanical activation.

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Two very different approaches to activate chemical bonds, nanoscale mechanochemistry and the ubiquitous thermochemistry, are studied and compared for a range of different thiolate/copper interfaces and junctions using self-assembled monolayers (SAMs) on perfect surfaces as well as single molecules anchored at steps and on clusters. In nanoscale mechanochemistry the activation proceeds by supplying locally pure mechanical energy to the desired atom(s) and/or bond(s). Using both dynamic and static electronic structure methods we predict vastly different reaction pathways and product classes for the two types of activation. These differences can be understood in terms of directional mechanical manipulation of coordination numbers and system fluctuations in the process of mechanical activation which affect the coupling of the thiolate molecular orbitals to the metal part of the molecule/metal junction or interface. The observed conceptual differences are huge in size and general in nature.

Manipulation is the most exciting feature of the non-contact atomic force microscopy technique as it allows building nanostructures on surfaces. Usually vertical manipulations are accompanied by an abrupt tip modification leading to a change of contrast. Here we report on low-temperature experiments demonstrating vertical manipulations of 'super'-Cu atoms on the p(2 Â 1) Cu(110):O surface, both extractions to and depositions from the tip, when the imaging contrast remains the same. These results are rationalized employing a novel and completely general method that combines density functional theory calculations for obtaining energy barriers as a function of tip height and a Kinetic Monte Carlo algorithm for studying the tip dynamics and extraction of manipulation statistics. The model reveals a novel multistep manipulation mechanism combining activated jumps of 'super'-Cu atoms to/from the tip with their drag by and diffusion on the tip.

Non-contact atomic force microscopy is used to measure the 3D force field on a dense-packed Cu(111) surface. An unexpected image contrast reversal is observed as the tip is moved towards the surface, with atoms appearing first as bright spots, whereas hollow and bridge sites turn bright at smaller tip-sample distances. Computer modeling is used to elucidate the nature of the image contrast. We find that the contrast reversal is essentially a geometrical effect, which, unlike in gold, is observable in Cu due to an unusually large stability of the tip-sample junction over large distances.

Antimony nanoparticles deposited under UHV conditions on HOPG are found to exhibit an intriguing frictional behavior characterized by a distinct clearly separated double dual behavior of dependence of the frictional force on contact area. We present the first realistic simulations, density functional modeling adapted to accommodate van der Waals interactions, of the (double) dual frictional behavior. The simulations provide insights into the physics/chemistry of all the frictional branches in terms of incommensurable interfaces, mobile spacer molecules as well as a novel concept of mobile oxidized multi-nanoasperities.