Identifying Multiple Configurations of Complex Molecules on Metal Surfaces

Abstract Experimental identification of molecular configurations in diffusion processes of large complex molecules has been a demanding topic in the field of molecular construction at solid surfaces. Such identification is needed in order to control the self‐assembly process and the properties and configurations of the resulting structures. This paper provides an overview of state‐of‐the‐art techniques for identification of molecular configurations in motion. First, a brief introduction to the conventional tools is presented, for example, low‐energy electron diffraction and IR/Raman spectroscopy. Second, currently used techniques, scanning probe microscopy, and its application in molecular configuration identification are reviewed. In the last part, a methodology combining time‐resolved tunneling spectroscopy and density functional theory calculation is reviewed in detail; this strategy has been successfully applied to two typical molecular systems, (t‐Bu)₄‐ZnPc and FePc (where Pc is phthalocyanine), with molecular rotation and laterial diffusion on the Au(111) surface.