Colliding molecules reveal their ‘cone of reaction’

For a chemical reaction to occur, atoms and molecules need to collide. However, not every collision produces a reaction. If the atoms and molecules are not favourably aligned with each other, nothing will happen. The “point of impact” of the colliding entities is also important, and it is hard to control because it requires confining the reactants along precise paths.

A team at the University of Graz, Austria, has now shed fresh light on this question by observing molecular coupling reactions on a single-crystal surface. “For the first time, we have been able to directly observe in real space and with single molecules which collision geometry must be met for a successful reaction,” explains Leonhard Grill, a physicist at Graz who co-led the study with post-doctoral researcher Matthew Timm. “Importantly, our experiment covers all geometric aspects of a reaction, namely, the precise location at which the reactants ‘touch’ each other upon collision, the ‘impact parameter’ (that is, how far the collision is from the reactants’ centre of mass) and the orientation of the reactants.”

Based on these observations, the researchers concluded that reactions only occur within a so-called “cone of reaction” that is defined by the colliding particles contacting at a specific point and a certain angle. This finding could lead to a better understanding of chemical reactions at the atomic scale and, ultimately, to ways of controlling and optimizing them.

Control of impact parameters

Grill and Timm used a scanning tunnelling microscope (STM) to project a molecule of difluorocarbene (CF2) onto a target radical (BTFyl) anchored to a copper surface. This set-up enabled them to control the impact parameter by launching the CF2 molecules directly and in a straight line along different atomic rows on the surface. They were also able to control the orientation of the BTFyl target by rotating it around its anchor point.

The researchers observed that reactions mainly occur when the CF2 approaches the BTFyl target on the same copper row to which the target is bound. This didn’t happen often. In fact, only six of the 79 collisions they observed – corresponding to a narrow range of impact parameters – resulted in a chemical reaction, and reactions did not happen at all when the orientation of the CF2 and the BTFyl deviated by more than 15 °.

“Controlling the impact parameter was for a long time considered to be the ‘forbidden fruit’ of reaction dynamics because of the technical difficulties to control it,” explains Grill. “The main challenge for us was how to do such experiments with relatively large molecules, which can have many adsorption orientations on the surface.”

A new view of collisions

Grill believes that the study’s findings could change the way we view collisions between reactants. “The new picture we have gleaned concerns not only the impact parameter, so where one reactant has to collide with another, but also the orientation of the involved compounds,” he tells Physics World. “If the reactants become larger and also have various side groups, understanding the cone of reaction might become even more important to understand, control and predict reaction rates.”

The researchers, who detail their work in Science, say they are already studying similar systems to assess whether the behaviour they observed can be generalized. In a related article, Jonas Björk of Linköping University, Sweden, suggests that further measurements could reveal how molecular structure, reactive sites and environment shape reaction pathways, enabling more predictive control of surface chemical transformations. “They could also enable single-molecule studies of how chirality influences chemical reactivity by directly controlling the handedness and orientation of reactants,” he adds.

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