Fabian Mohn

The Chemical Structure of a Molecule Resolved by Atomic Force Microscopy

Atomic Imaging Within Adsorbed Molecules Scanning tunneling microscopy provides atomic resolution images of surfaces and adsorbed atoms, but imaging atoms within an organic molecule adsorbed on a surface is difficult because contrast is lacking in the states that determine the tunneling current. Atomic force microscopy should be able to resolve atoms through changes in short-range chemical forces, but resolution is lost if the scanning tip undergoes modifications or if it moves the molecule. Gross et al. (p. 1110) show that in situ functionalization of the tip—for example, with CO—can dramatically improve the resolution of images of pentacene molecules adsorbed on conducting surfaces, like copper, and nonconductors, like NaCl. Derivitization of atomic force microscope tips with carbon monoxide molecules allows atoms to be resolved within adsorbed molecules. Resolving individual atoms has always been the ultimate goal of surface microscopy. The scanning tunneling microscope images atomic-scale features on surfaces, but resolving single atoms within an adsorbed molecule remains a great challenge because the tunneling current is primarily sensitive to the local electron density of states close to the Fermi level. We demonstrate imaging of molecules with unprecedented atomic resolution by probing the short-range chemical forces with use of noncontact atomic force microscopy. The key step is functionalizing the microscope’s tip apex with suitable, atomically well-defined terminations, such as CO molecules. Our experimental findings are corroborated by ab initio density functional theory calculations. Comparison with theory shows that Pauli repulsion is the source of the atomic resolution, whereas van der Waals and electrostatic forces only add a diffuse attractive background.

Bond-order discrimination by atomic force microscopy.

Visualizing Bond Order Bond lengths in conjugated molecules closely reflect individual bond order and are usually determined by diffraction methods. It is valuable to know bond order for rationalizing aromaticity, and reactivity and for chemical structure determination. Gross et al. (p. 1326; see the Perspective by Perez and the cover) differentiated the bond orders in individual molecules in the fullerene C60 and in polyaromatic hydrocarbons by imaging with noncontact atomic force microscopy (AFM). The molecules were adsorbed onto a copper surface, and the AFM tip was decorated with a CO molecule, which was used to measure tip frequency shifts above the bonds and their apparent lengths. Multiple bonds appeared brighter in the images because of stronger Pauli repulsion, and their shorter length was amplified by bending of the CO at the tip apex. Images detected with an atomic force microscope tip decorated with a carbon monoxide molecule could distinguish Pauling bond order. We show that the different bond orders of individual carbon-carbon bonds in polycyclic aromatic hydrocarbons and fullerenes can be distinguished by noncontact atomic force microscopy (AFM) with a carbon monoxide (CO)–functionalized tip. We found two different contrast mechanisms, which were corroborated by density functional theory calculations: The greater electron density in bonds of higher bond order led to a stronger Pauli repulsion, which enhanced the brightness of these bonds in high-resolution AFM images. The apparent bond length in the AFM images decreased with increasing bond order because of tilting of the CO molecule at the tip apex.

Organic structure determination using atomic-resolution scanning probe microscopy

Nature offers a huge and only partially explored variety of small molecules with potential pharmaceutical applications. Commonly used characterization methods for natural products include spectroscopic techniques such as nuclear magnetic resonance spectroscopy and mass spectrometry. In some cases, however, these techniques do not succeed in the unambiguous determination of the chemical structure of unknown compounds. To validate the usefulness of scanning probe microscopy as an adjunct to the other tools available for organic structure analysis, we used the natural product cephalandole A, which had previously been misassigned, and later corrected. Our results, corroborated by density functional theory, demonstrate that direct imaging of an organic compound with atomic-resolution force microscopy facilitates the accurate determination of its chemical structure. We anticipate that our method may be developed further towards molecular imaging with chemical sensitivity, and will become generally useful in solving certain classes of natural product structures.

Measuring the Charge State of an Adatom with Noncontact Atomic Force Microscopy

Spotting Charges Many nanoscale physical systems are sensitive to the position of isolated charges, such as single-electron transistors and molecular assemblies that separate charges with energy from photons. In order to probe the location of a charged atom, the most general methods would work on insulating surfaces. Gross et al. (p. 1428; see the Perspective by Meyer and Glatzel) show that a tuning-fork atomic force microscope (AFM) operating in a noncontact mode at cryogenic temperatures can resolve the charge state of gold and silver atoms absorbed on a sodium chloride film. Charged atoms set up image charges in the AFM tip, which creates an electrostatic force not present with a neutral atom. Charging of gold and silver atoms on salt films changes the force detected by the tip of a scanning probe microscope. Charge states of atoms can be investigated with scanning tunneling microscopy, but this method requires a conducting substrate. We investigated the charge-switching of individual adsorbed gold and silver atoms (adatoms) on ultrathin NaCl films on Cu(111) using a qPlus tuning fork atomic force microscope (AFM) operated at 5 kelvin with oscillation amplitudes in the subangstrom regime. Charging of a gold atom by one electron charge increases the force on the AFM tip by a few piconewtons. Moreover, the local contact potential difference is shifted depending on the sign of the charge and allows the discrimination of positively charged, neutral, and negatively charged atoms. The combination of single-electron charge sensitivity and atomic lateral resolution should foster investigations of molecular electronics, photonics, catalysis, and solar photoconversion.

Imaging the charge distribution within a single molecule

Scanning tunnelling microscopy and atomic force microscopy can be used to study the electronic and structural properties of surfaces, as well as molecules and nanostructures adsorbed on surfaces, with atomic precision, but they cannot directly probe the distribution of charge in these systems. However, another form of scanning probe microscopy, Kelvin probe force microscopy, can be used to measure the local contact potential difference between the scanning probe tip and the surface, a quantity that is closely related to the charge distribution on the surface. Here, we use a combination of scanning tunnelling microscopy, atomic force microscopy and Kelvin probe force microscopy to examine naphthalocyanine molecules (which have been used as molecular switches) on a thin insulating layer of NaCl on Cu(111). We show that Kelvin probe force microscopy can map the local contact potential difference of this system with submolecular resolution, and we use density functional theory calculations to verify that these maps reflect the intramolecular distribution of charge. This approach could help to provide fundamental insights into single-molecule switching and bond formation, processes that are usually accompanied by the redistribution of charge within or between molecules.

The mechanisms underlying the enhanced resolution of atomic force microscopy with functionalized tips

By functionalizing the tip of an atomic force microscope (AFM) with a molecule or an atom that significantly contributes to the tip–sample interaction, the resolution can be dramatically enhanced. The interaction and therefore the resolution crucially depend on the chemical nature of the tip termination. Employing a tip functionalized with a CO molecule, atomic resolution of a pentacene molecule was recently demonstrated. In this work, the interaction between the CO tip and the pentacene imaged are studied with first principles calculations. The calculated frequency shifts compare very well with the experiment. The different energy contributions are analyzed and the Pauli energy is computed. We demonstrate that the source of the high resolution is Pauli repulsion, whereas van der Waals and electrostatic interactions only add a diffuse attractive background.

Reversible Bergman cyclization by atomic manipulation

The Bergman cyclization is one of the most fascinating rearrangements in chemistry, with important implications in organic synthesis and pharmacology. Here we demonstrate a reversible Bergman cyclization for the first time. We induced the on-surface transformation of an individual aromatic diradical into a highly strained ten-membered diyne using atomic manipulation and verified the products by non-contact atomic force microscopy with atomic resolution. The diyne and diradical were stabilized by using an ultrathin NaCl film as the substrate, and the diyne could be transformed back into the diradical. Importantly, the diradical and the diyne exhibit different reactivity, electronic, magnetic and optical properties associated with the changes in the bond topology, and spin multiplicity. With this reversible, triggered Bergman cyclization we demonstrated switching on demand between the two reactive intermediates by means of selective C-C bond formation or cleavage, which opens up the field of radical chemistry for on-surface reactions by atomic manipulation.

Different tips for high-resolution atomic force microscopy and scanning tunneling microscopy of single molecules

We explore different tip functionalizations for atomic force microscopy (AFM), scanning tunneling microscopy (STM), and Kelvin probe force microscopy (KPFM) of organic molecules on thin insulating films. We describe in detail how tips terminated with single Br and Xe atoms can be created. The performance of these tips in AFM, STM, and KPFM imaging of single molecules is compared to other tip terminations, and the advantages and disadvantages of the different tips are discussed. The Br tip was found to be particularly useful for AFM and lateral manipulation, whereas the Xe tip excelled in STM and KPFM.

A Combined Atomic Force Microscopy and Computational Approach for the Structural Elucidation of Breitfussin A and B: Highly Modified Halogenated Dipeptides from Thuiaria breitfussi

The use of atomic-force microscopy (AFM) with atomic resolution shows great potential for the structural characterization of planar, proton-poor compounds, as these compounds are prone to structural corrections. [1,2] Currently, AFM has limited ability to identify element type and consequently functional groups. Additional computational techniques, such as computer-aided structure elucidation (CASE) and the calculation of 13 C NMR shifts using electronic structure calculations (DFT) may assist in this respect. Herein we show the combined use of spectroscopic methods, AFM, CASE, and DFT to solve the structures of breitfussins A and B, which could not be solved using either method alone. The subject of this study was the Arctic hydrozoan Thuiaria breitfussi (Family Sertulariidae). The few publications on the chemistry of this family show the presence of sterols, [3] polyhalogenated monoterpenes, [4] and anthracenone derivatives. [5] Arctic marine environments support highly diverse and dense populations of marine invertebrates. [6,7] A

Measuring the short-range force field above a single molecule with atomic resolution

We present a method that enables atomic-resolution measurements of the short-range force field above a single organic admolecule using noncontact atomic force microscopy. We have extended the standard force-mapping technique to be able to measure at close tip–molecule distances, in regions that cannot be accessed by normal constant-height or constant-frequency-shift imaging. Our technique can be used to study the interaction between a well-defined scanning probe tip and an admolecule on the atomic scale and yields atomic resolution of both molecule and substrate. Furthermore, it enables the measurement of constant-frequency-shift topographies of molecules with nonplanar adsorption geometries.