Scanning Tunneling Microscopy and Atomic Force Microscopy in Organic Chemistry

When Kekulé awoke from dreams of snakes biting their own tails, he didn't have the benefit of a scanning tunneling microscope (STM) image to confirm that his vision of benzene as a cyclic molecule was accurate. References to STM in the chemical literature increase steadily, although the technique was perhaps oversold in its early days of the 1980s, with such promises as DNA sequencing and tailored bi‐molecular chemical reactions (literally, two molecules). Publications alternate between attempting to explain the process by which images of traditional insulators are obtained and simply presenting the end images themselves as stunning views of atoms and molecules. While imaging mechanisms are still being debated, these instruments' ability to “see” single molecules has been established, albeit at the fringes of our expectations. For example, whereas STM studies at present might not be able to answer the question of why adsorption of CO doubles the density of platinum atoms on the surface of a single crystal of the metal, the images go far in illustrating that this is a process which platinum undergoes. As with any emerging analytical tool, these scanning, very localized microscopic methods are undergoing the growing pains of irreproducible results and mis‐marketed artifacts. Nonetheless, we assemble here, primarily for the uninitiated, a collection of careful and credible studies to mark the progress of scanning tunneling microscopy and atomic force microscopy into chemistry, and to encourage a healthy blend of idealism and skepticism toward future work.