The atomic force microscope (AFM) was conceived to image surfaces of insulators with the atomic resolution that a scanning tunneling microscope (STM) had already provided for metal and semiconductor surfaces.  In the meantime, scanning probe methods have turned into prime tools for quantum physics and chemistry at surfaces and interfaces.  Besides the capability of modern instruments to design matter atom by atom, this stupendous development is due to the invention of a rapidly oscillating piezoceramic tuning fork as a force probe and the functionalization of the microscope tips with specific atoms or molecules.  These features were used to probe for the first time the local chemical reactivity within a single molecule in challenging experiments where the spatial separation of two atoms is reduced to less than a bonding length.

A single CO molecule that is transferred from a surface to the microscope tip applying known protocols acts as the sensor for chemical reactivity.  Figure 1 illustrates the procedure of picking up a single CO from the surface.  To this end, an ensemble of CO molecules is coadsorbed with the target molecule to be studied.  In STM images, a single CO molecule appears as a circular depression (arrow in Figure 1a).  Upon sufficiently close approach to an adsorbed CO the biased tip is decorated with the CO.  The resulting tip carries a single CO molecule where the O atom constitutes the outmost apex atom.  The successful transfer is proved by the henceforth missing CO on the surface and the increased spatial resolution of the target molecules (Figure 1b, Figure 1b*) as well as by the appearance of adsorbed CO as circular protrusions (Figure 1c).


Figure 1: Functionalization of an STM metal tip with a single CO molecule. (a) STM image of a Ag(111) terrace with 4 2H-Pc molecules and 1 CO molecule (arrow) (50 mV, 15 pA, 21 nm × 13 nm) acquired with a metal tip. (b) Same STM image as in (a) acquired with a CO-terminated tip. (c) The CO-terminated tip images adsorbed CO molecules as protrusions (dashed circles) rather than depressions (a) (50 mV, 15 pA, 9 nm × 14 nm). The bottom row schematically illustrates the process of picking up an adsorbed CO with the STM tip. The inset (b*) demonstrates the increased spatial resolution of an adsorbed 2H-Pc when imaged with a CO-terminated tip.

This tip is now used to explore the local chemical reactivity of a simple dye.  In the present case, it is a phthalocyanine (2H-Pc, Figure 2a) that appears with a characteristic cloverlike shape in STM images (Figure 1, Figure 2a (left panel)).  The key experimental findings that support the idea of a single-molecule probe for intramolecular chemical reactivity are depicted in Figure 2b.  They show that the evolution of the short-range force between the CO probe and 2H-Pc depends on the actual approached intramolecular site.  The data sets reveal for two exemplary sites that the point of maximum attraction (force minimum marked (z*,F*)) exhibits a significantly stronger force F* at the macrocyclic center (red dot in the AFM image of Figure 2a) than at its periphery (blue).  The hypothesis that F* represents an indicator for the local chemical reactivity has been corroborated in additional experiments.

Figure 2: (a) Model of the phthalocyanine dye 2H-Pc together with an STM (left, 100 mV, 50 pA, apparent heights range from 0 pm (dark blue) to 100 pm (white)) and an AFM (right, gray scales encode resonance frequency changes from −13 Hz (dark) to −7 Hz (bright)) image of a single 2H-Pc adsorbed on Ag(111). (b) Short-range forces between a CO-terminated tip and the center of a benzene moiety (top) and the molecular center (bottom). These sites are indicated in the AFM image of (a). The approach direction is marked as the horizontal arrow. Tip displacement z* marks the point of maximum attraction with force F*. Zero distance is defined by the tip displacement at which the feedback loop was deactivated above clean Ag(111) (50 mV, 15 pA).

The macrocyclic center of 2H-Pc becomes more reactive upon removal of the pyrrolic H.  Indeed, it is known from conventional chemical experiments with a multitude of phthalocyanines that the encapsulation of a metal atom into the molecular center – the metalation reaction of the dye – evidences its increased chemical reactivity.  The H atoms can be removed in an atom-by-atom fashion using the scanning probe tip; that is, the chemical reaction 2H-Pc → H-Pc → Pc can be manually performed at the single-molecule level.   In that manner, the chemical reactivity of the center can be varied atom by atom.  Figure 3a shows an STM and AFM image of the resulting product molecule Pc.  As demonstrated in Figure 3b, the short-range force at the point of maximum attraction between CO and the macrocyclic center (bottom data set in Figure 3b) is indeed substantially stronger than observed from 2H-Pc.  The additional experiments corroborate that the magnitude of F* represents a viable quantitative measure for the local chemical reactivity.

Figure 3: As Figure 2 for Pc.

In conclusion, the presented experiments reveal that a single CO molecule serves as a sensitive probe for the local chemical reactivity.  The magnitude of the maximum short-range attraction between the molecular sensor and the explored molecule is a quantitative measure for the strength of the bond; the larger |F*| the more reactive is the investigated intramolecular site.  These novel findings open the path to detect with atomic resolution the reactive centers of biologically and chemically relevant molecules.  Future nanotechnologies that aim at the construction and application of functional molecules may benefit from these results.

The American Chemical Society has recently published the findings in The Journal of Physical Chemistry Letters:

K. Rothe, N. Néel, M.-L. Bocquet, J. Kröger, Extraction of Chemical Reactivity and Structural Relaxations of an Organic Dye from the Short-Range Interaction with a Molecular Probe, J. Phys. Chem. Lett. 13, 8660 (2022).



Prof. Dr. Jörg Kröger
Technische Universität Ilmenau
Department of
Mathematics and Natural Sciences
Group Experimental Physics I / Surface Physics