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Self-assembled monolayers of ferrocenecarboxylic acid (FcCOOH) contain two fundamental units, both stabilized by intermolecular hydrogen bonding: dimers and cyclic five-membered catemers. At surface coverages below a full monolayer, however, there is a significantly more varied structure that includes double-row clusters containing two to twelve FcCOOH molecules. Statistical analysis shows a distribution of cluster sizes that is sharply peaked compared to a binomial distribution. This rules out simple nucleation-and-growth mechanisms of cluster formation, and strongly suggests that clusters are formed in solution and collapse into rows when deposited on the Au(111) surface. [ABSTRACT FROM AUTHOR]

The authors have developed a method of performing scanning tunneling microscopy experiments with a sample that can be controllably heated and quickly cooled. Temperatures in excess of 100 °C are achievable, and the same scanning area can be imaged multiple times before and after repeated heating cycles. This opens up for study any physical process or chemical reaction where the reactants, products, and/or intermediates can be kinetically trapped on a conductive surface at room temperature. As a demonstration of this approach, the authors have investigated desorption from 1-octanethiolate self-assembled monolayers on Au(111). [ABSTRACT FROM AUTHOR]

Three-dimensional (3D) printing has many advantages over conventional machining techniques, and it is particularly well suited for rapid production of prototypes. This Shop Note reports pumpdown curves for a small ultrahigh-vacuum chamber loaded with 3D-printed silver and titanium parts. Neither material showed any measurable adverse affect on the ultimate base pressure achieved, which was approximately 5×10-10 Torr. 3D-printed metals can therefore be considered suitable for select ultrahigh-vacuum applications. [ABSTRACT FROM AUTHOR]

Molecular self-assembly is driven by intermolecular interactions between the functional groups on the component molecules. Small changes in molecular structure can make large differences in extended structure, and understanding this connection will lead to predictive power and control of the self-assembly process. Scanning tunneling microscopy is used to study self-assembly in two-dimensional clusters and monolayers, and the experimental approach is to study "families" of molecules where one or more functional groups is varied in a methodical way. Studied families include indole carboxylic acids, isatin derivatives (which have the indole backbone), quinaldic acid, thioethers, and fluorenone derivatives. In these systems, a variety of intermolecular interactions drive the assembly of the molecular monolayer, including hydrogen bonds, van der Waals forces, zwitterionic interactions, surface interactions, and halogen interactions.

Scanning tunneling microscopy images of diferrocenylacetylene (DFA) coadsorbed with benzene on Au(111) show individual and close-packed DFA molecules, either adsorbed alongside benzene or on top of a benzene monolayer. Images acquired over a range of positive and negative tip-sample bias voltages show a shift in contrast, with the acetylene linker appearing brighter than the ferrocenes at positive sample bias (where unoccupied states primarily contribute) and the reverse contrast at negative bias. Density functional theory was used to calculate the electronic structure of the gas-phase DFA molecule, and simulated images produced through two-dimensional projections of these calculations approximate the experimental images. The symmetry of both experimental and calculated molecular features for DFA rules out a cis adsorption geometry, and comparison of experiment to simulation indicates torsion around the inter-ferrocene axis between 90° and 180° (trans); the cyclopentadienyl rings are thus angled with respect to the surface.

Ultrahigh-vacuum scanning tunneling microscopy (STM) was used to study trans-[Cl(dppe)2Ru(C Triple Bond C)6Ru(dppe)2Cl] [abbreviated as Ru2, diphenylphosphinoethane (dppe)] on Au(111). This large organometallic molecule was pulse deposited onto the Au(111) surface under ultrahigh-vacuum (UHV) conditions. UHV STM studies on the prepared sample were carried out at room temperature and 77 K in order to probe molecular adsorption and to characterize the surface produced by the pulse deposition process. Isolated Ru2 molecules were successfully imaged by STM at room temperature; however, STM images were degraded by mobile toluene solvent molecules that remain on the surface after the deposition. Cooling the sample to 77 K allows the solvent molecules to be observed directly using STM, and under these conditions, toluene forms organized striped domains with regular domain boundaries and a lattice characterized by 5.3 and 2.7 A intermolecular distances. When methylene chloride is used as the solvent, it forms analogous domains on the surface at 77 K. Mild annealing under vacuum causes most toluene molecules to desorb from the surface; however, this annealing process may lead to thermal degradation of Ru2 molecules. Although pulse deposition is an effective way to deposit molecules on surfaces, the presence of solvent on the surface after pulse deposition is unavoidable without thermal annealing, and this annealing may cause undesired chemical changes in the adsorbates under study. Preparation of samples using pulse deposition must take into account the characteristics of sample molecules, solvent, and surfaces.