Over the past two decades, interest in the self-assembly of organic molecules on solid metal substrates has grown considerably, driven by an opportunity to develop inexpensive, tunable organic optoelectronic devices. Such systems synergistically combine the electrical conductivity of the metal with the highly tunable properties of organic molecules, enabling the potential for new properties and functionalities not possessed by either material separately. The high sensitivity of the electronic and optical properties of the material to the choice of adsorbate highlights the advantage of optimizing the adsorbate/substrate pair when designing organic electronic materials. The advancement of Organic Light Emission Diodes (OLEDs) and Organic Field Effect Transistors (OFETs) to the market highlights the promise and versatility of organic optoelectronic devices. However, there is still much work to be done in developing a molecular-level understanding of the chemical and electronic nature of the interface, the impact of the identity of the substrate and adsorbate pair, and the distinct substrate/adsorbate interactions. The large size of the minimum representative unit and the complex interactions (e.g. covalent bonding, van der Waals, charge transfer, Pauli repulsion) in such systems have made modelling the structure and stability of such systems challenging. Recent progress in computational capability has made feasible the application of computational techniques involving quantum mechanical approaches, such as density functional theory (DFT) and ab initio molecular dynamics (AIMD), to these systems.