A detailed review of the literature for the last 5-10 years on epitaxial growth of graphene is presented. Both experimental and theoretical aspects related to growth on transition metals and on silicon carbide are thoroughly reviewed. Thermodynamic and kinetic aspects of growth on all these materials, where possible, are discussed. To make this text useful for a wider audience, a range of important experimental techniques that have been used over the last decade to grow (e.g. CVD, TPG and segregation) and characterize (STM, LEEM, etc.) graphene are reviewed, and a critical survey of the most important theoretical techniques is given. Finally, we critically discuss various unsolved problems related to growth and its mechanism which we believe require proper attention in future research.

We report on a joint experimental and theoretical study of the ordered structures of melamine molecules formed on the Au( 111)-( 22× 3) surface. Scanning tunneling microscopy (STM) images taken under UHV conditions reveal two distinct monolayers one of which has never been reported before on gold. We also find that one of the structures may serve as a transition region ("domain wall") between islands formed by the other arrangement. Using state-of-the-art density functional calculations in conjunction with a systematic gas-phase analysis based on considering all planar structures melamine molecules can form with each other, we propose atomistic models for both structures and the transition region.

Nonsymmetrical organic molecules adsorbed on solid surfaces may assemble into random networks, thereby providing model systems for organic glasses that can be directly observed by scanning tunneling microscopy (STM). We investigated the structure of a disordered cytosine network on a gold(111) surface created by thermal quenching, to temperatures below 150 K, of the two-dimensional fluid present on the surface at room temperature. Comparison of STM images to density functional theory calculations allowed us to identify three elementary structural motifs (zigzag filaments and five- and six-membered rings) that underlie the whole supramolecular random network. The identification of elementary structural motifs may provide a new framework for understanding medium-range order in amorphous and glassy systems.

Hydrogen bonding underpins the properties of a vast array of systems spanning a wide variety of scientific fields. From the elegance of base pair interactions in DNA to the symmetry of extended supramolecular assemblies, hydrogen bonds play an essential role in directing intermolecular forces. Yet fundamental aspects of the hydrogen bond continue to be vigorously debated. Here we use dynamic force microscopy (DFM) to quantitatively map the tip-sample force field for naphthalene tetracarboxylic diimide molecules hydrogen-bonded in two-dimensional assemblies. A comparison of experimental images and force spectra with their simulated counterparts shows that intermolecular contrast arises from repulsive tip-sample interactions whose interpretation can be aided via an examination of charge density depletion across the molecular system. Interpreting DFM images of hydrogen-bonded systems therefore necessitates detailed consideration of the coupled tip-molecule system: analyses based on intermolecular charge density in the absence of the tip fail to capture the essential physical chemistry underpinning the imaging mechanism.