Molecular nanofabrication with a scanning probe microscope (SPM) is a promising route toward the prototyping of metastable functional molecular structures and devices which do not form spontaneously. The aspect of mechanical stability is crucial for such structures, especially if they extend into the third dimension vertical to the surface. A prominent example is freestanding molecules fabricated on a metal which can function as field emitters or electric field sensors. Improving the stability of such molecular configurations is an optimization task involving many degrees of freedom and therefore best tackled by computational nanostructure design. Here, we use density functional theory to study 3,4,9,10-perylene-tetracarboxylic dianhydride (PTCDA) standing on the Ag(111) surface as well as on the tip of a scanning probe microscope. We cast our results into a simple set of design principles for such metastable structures, the validity of which we subsequently demonstrate in two computational case studies. Our work proves the capabilities of computational nanostructure design in the field of metastable molecular structures and offers the intuition needed to fabricate new devices without tedious trial and error.
© 2022 The Authors. Published by American Chemical Society.