Cyclo[18]carbon (C₁₈, a molecular carbon allotrope) can be synthesized by dehalogenation of a bromocyclocarbon precursor, C₁₈Br₆, in 64% yield, by atomic manipulation on a sodium chloride bilayer on Cu(111) at 5 K, and imaged by high-resolution atomic force microscopy. This method of generating C₁₈ gives a higher yield than that reported previously from the cyclocarbon oxide C₂₄O₆. The experimental images of C₁₈ were compared with simulated images for four theoretical model geometries, including possible bond-angle alternation: D_18h cumulene, D_9h polyyne, D_9h cumulene, and C_9h polyyne. Cumulenic structures, with (D_9h) and without (D_18h) bond-angle alternation, can be excluded. Polyynic structures, with (C_9h) and without (D_9h) bond-angle alternation, both show a good agreement with the experiment and are challenging to differentiate.

We designed and studied hydrocarbon model compounds by high-resolution noncontact atomic force microscopy. In addition to planar polycyclic aromatic moieties, these novel model compounds feature linear alkyl and cycloaliphatic motifs that exist in most hydrocarbon resources - particularly in petroleum asphaltenes and other petroleum fractions - or in lipids in biological samples. We demonstrate successful intact deposition by sublimation of the alkyl-aromatics, and differentiate aliphatic moieties from their aromatic counterparts which were generated from the former by atomic manipulation. The characterization by AFM in combination with atomic manipulation provides clear fingerprints of the aromatic and aliphatic moieties that will facilitate their assignment in a priori unknown samples.

Dissolved organic carbon (DOC) is the largest pool of exchangeable organic carbon in the ocean. However, less than 10% of DOC has been molecularly characterized in the deep ocean to understand DOC's recalcitrance. Here we analyze the radiocarbon (14C) depleted, and presumably refractory, low molecular weight (LMW) DOC from the North Central Pacific using atomic force microscopy to produce the first atomic-resolution images of individual LMW DOC molecules. We evaluate surface and deep LMW DOC chemical structures in the context of their relative persistence and recalcitrance. Atomic force microscopy resolved planar structures with features similar to polycyclic aromatic compounds and carboxylic-rich alicyclic structures with less than five aromatic carbon rings. These compounds comprise 8% and 20% of the measurable molecules investigated in the surface and deep, respectively. Resolving the structures of individual DOC molecules represents a step forward in molecular characterization of DOC and in understanding its long-term stability.