If you have an ACS member number, please enter it here so we can link this account to your membership. (optional)

ACS values your privacy. By submitting your information, you are gaining access to C&EN and subscribing to our weekly newsletter. We use the information you provide to make your reading experience better, and we will never sell your data to third party members.


Physical Chemistry

A New Molecular Dynamic Frontier

New experiments show bond excitation can lead to counterintuitive products

by Elizabeth K. Wilson
July 20, 2009 | A version of this story appeared in Volume 87, Issue 29

Although the C–H bond in this reaction is excited, it unexpectedly does not break. Rather, the reaction products favor DF + CHD2.
Although the C–H bond in this reaction is excited, it unexpectedly does not break. Rather, the reaction products favor DF + CHD2.

A provocative new study shows that, contrary to previous experimental results, exciting a stretching mode of a bond in a molecule during a particular simple chemical reaction does not break the excited bond. In fact, the reaction rate slows, and unexpected products form. The result lays open a vast new territory waiting to be explored: one of energy distribution and transfer during molecular dynamics.

Researcher Kopin Liu and colleagues Hiroshi Kawamata and Weiqing Zhang of Academia Sinica, in Taiwan, show that exciting the C–H stretching mode in the exothermic reaction F + CHD3 not only leads to unexpected products DF + CHD2 but also slows the reaction rate (Science 2009, 325, 303).

Most experiments that selectively excite the stretching mode of a particular bond in simple chemical reactions have been on endothermic reactions, and the process breaks the excited bond. For example, exciting the CD bond during the reaction CH3D + Cl leads to the products CH3 + DCl.

Although the precise mechanism of this new exothermic reaction has yet to be elucidated, the authors posit that exciting the C–H stretching mode enacts a host of controls on the reaction, including, perhaps, blocking energetic channels that would have ordinarily permitted the breaking of the C–H bond, transferring energy to other parts of the system, and slowing the reaction.

The new work is "beautiful," says University of Wisconsin, Madison, chemistry professor F. Fleming Crim, whose lab has been at the forefront of selective bond excitation chemistry. "These incisive experiments reveal the complexity of reactions of polyatomic molecules," Crim says. "Experiments such as Kopin's move us toward that goal and call on theory to help build models of this more complex behavior."


This article has been sent to the following recipient:

Chemistry matters. Join us to get the news you need.