Force-isosurface simulations probe the limits of high-resolution AFM on three-dimensional molecules.

Abstract

High-resolution atomic force microscopy has transformed molecular imaging by revealing intramolecular structure directly in real space. A major remaining challenge is to extend this capability from largely planar molecules to non-planar molecular systems, where the most important structural information may be distributed across different heights above the surface. Here we use probe-particle-model simulations to predict the constant-force contours expected above molecules with increasing structural complexity. By extractingisosurfaces from simulated three-dimensional force fields, we compare the molecular information retained in constant-height and constant-force images. For tilted benzene and pyrrole, constant-force images preserve the molecular framework across a range of adsorption angles and allow the molecular orientation to be recovered quantitatively. For larger non-planar and three-dimensional systems, simulations identify characteristicisosurface contrast associated with adsorption geometry, lower-lying molecular structure and curved molecular surfaces. These results provide target contrast patterns forisosurfaces obtainable from three-dimensional force-mapping experiments and quantify the molecular information retained by idealisosurface imaging as molecular systems become progressively non-planar.