Scanning tunneling microscopy and local conductance mapping show spin-state coexistence in bilayer films of Fe[(H2Bpz2)2bpy] on Au(111) that is independent of temperature between 131 and 300 K. This modification of bulk behavior is attributed in part to the unique packing constraints of the bilayer film that promote deviations from bulk behavior. The local density of states measured for different spin states shows that high-spin molecules have a smaller transport gap than low-spin molecules and are in agreement with density functional theory calculations.

We present a novel technique of growing UHV graphene using atomic hydrogen etching of SiC(0001)–Si surfaces. Hydrogen atoms generated from a hot tungsten filament selectively etch silicon surface atoms thereby facilitating the Si-sublimation process at temperatures around 1000 °C according to Auger Electron Spectroscopy. This allows for separate, non-thermal control of the rate of formation of the interfacial buffer layer formation to yield reduced pit formation observed by scanning tunneling microscopy during subsequent UHV graphene growth.

Scanning tunneling microscopy studies of the first monolayer of 2,8-difluoro-5,11-(bis)triethylsilylethynyl anthradithiophene on Au(111) reveal two ordered structures with anthradithiophene planes parallel to the substrate. Submolecular resolution STM images demonstrate structures with a close approach of fluorine–sulfur and fluorine–fluorine atoms in the ordered structures. This provides evidence for the importance of noncovalent F–S and F–F in driving 2D self-assembly in the monolayer. Spectroscopic studies indicate a transport gap of 2.4 eV that is insensitive to the local domain structures, as expected for weak intermolecular interactions.

Scanning tunneling microscopy is used to observe the structure of the first monolayer of Alq3 on Cu(1 1 0). Individual molecules can be resolved at very low coverage where there is also evidence of significant surface mobility. As Alq3 surface coverage increases, molecules aggregate by forming pairs and chain-like structures without ever establishing long range order. Interfacial disorder is maintained even after annealing to 590 K. The tendency to form chain-like aggregates is attributed to anisotropic intermolecular interactions. Anisotropies in these interactions are implicated in chain formation by illustrative density functional theory calculations and the role of direct dipolar interactions, anisotropic van der Waals interactions, and substrate-mediated interactions is discussed.Graphical abstractHighlights► Alq3 molecules on Cu(1 1 0) visualized with STM. ► First layer is strongly disordered. ► Chain-like aggregates form due to anisotropic intermolecular interactions.

Image potential-derived states of upright chemisorbed benzoate molecules on a Cu(110) surface have been measured with scanning tunneling spectroscopy. The widths of image-derived features for these adsorbates are sensitive to the presence of coexisting flat-lying benzoate molecules. This dependence is attributed to the different couplings between image potential state wave functions and bulk metal states that result from differences in substrate-mediated intermolecular interactions. The comparative trends are semiquantitatively modeled using a dielectric continuum approach.Keywords (keywords): molecular assembly; scanning tunneling spectroscopy;