Those special molecules comprise the "first solvation shell," and although it has been known for decades that they can sense and dictate the fate of nearly every chemical reaction, it has been virtually impossible to watch them respond. University of Michigan researchers Kevin Kubarych and Carlos Baiz, however, recently achieved the feat. Their work was published online Aug. 25 in the Journal of the American Chemical Society.
Until now, observing the solvent shell in action has been difficult for several reasons. First, fundamental steps in chemical reactions are exceedingly fast. To "film" a chemical reaction requires a camera with a "shutter speed" of femtoseconds (one femtosecond is the time it takes light to travel the length of a bacterium---about half a micrometer, or one hundredth the width of a human hair).
Second, a solution contains many solvent molecules, but only a few are privileged to be in the first solvation shell and participate in the reaction. Finally, most spectroscopic probes of liquids are not chemically specific, meaning they can't identify the particular molecular species they are monitoring.
To sum up, watching the first solvation shell respond to a chemical reaction requires a combination of ultrafast time resolution and the ability to initiate the reaction and track the solvent shell's response. It is this combination that Kubarych, an assistant professor of chemistry, and graduate student Baiz have achieved.
The key breakthrough was to realize that electrons move during chemical reactions and that when the nearest solvent molecules sense the electron redistribution, their vibrational frequencies change. Much as the strings on a musical instrument are intimately connected to the wooden neck and body, the solvent shell and the reacting molecule are tightly coupled and difficult to disentangle. Indeed, the very act of holding an instrument may cause it to warp or heat up and, in principle, these changes affect the frequencies of vibration of the strings. Similarly, the new approach to reaction dynamics introduced by Kubarych's lab essentially "listens" to the very fastest events in chemical reactions by noting the changing resonance frequencies of the surrounding molecules.
"This level of detailed information on the complex environments common in chemical transformations is unique," Kubarych said, "and promises to offer remarkable insight into the understanding of natural and artificial charge transfer reactions—processes that are of fundamental importance in contexts ranging from cellular respiration to solar energy conversion."
The research was supported by the National Science Foundation and the U-M Rackham Graduate School.
For more information on Kubaraych: https://www.chem.lsa.umich.edu/chem/faculty/facultyDetail.php?Uniqname=kubarych
Journal of the American Chemical Society: http://pubs.acs.org/journal/jacsat
Nancy Ross-Flanigan | Newswise Science News
Researchers identify potentially druggable mutant p53 proteins that promote cancer growth
09.12.2016 | Cold Spring Harbor Laboratory
Plant-based substance boosts eyelash growth
09.12.2016 | Fraunhofer-Institut für Angewandte Polymerforschung IAP
Physicists of the University of Würzburg have made an astonishing discovery in a specific type of topological insulators. The effect is due to the structure of the materials used. The researchers have now published their work in the journal Science.
Topological insulators are currently the hot topic in physics according to the newspaper Neue Zürcher Zeitung. Only a few weeks ago, their importance was...
In recent years, lasers with ultrashort pulses (USP) down to the femtosecond range have become established on an industrial scale. They could advance some applications with the much-lauded “cold ablation” – if that meant they would then achieve more throughput. A new generation of process engineering that will address this issue in particular will be discussed at the “4th UKP Workshop – Ultrafast Laser Technology” in April 2017.
Even back in the 1990s, scientists were comparing materials processing with nanosecond, picosecond and femtosesecond pulses. The result was surprising:...
Have you ever wondered how you see the world? Vision is about photons of light, which are packets of energy, interacting with the atoms or molecules in what...
A multi-institutional research collaboration has created a novel approach for fabricating three-dimensional micro-optics through the shape-defined formation of porous silicon (PSi), with broad impacts in integrated optoelectronics, imaging, and photovoltaics.
Working with colleagues at Stanford and The Dow Chemical Company, researchers at the University of Illinois at Urbana-Champaign fabricated 3-D birefringent...
In experiments with magnetic atoms conducted at extremely low temperatures, scientists have demonstrated a unique phase of matter: The atoms form a new type of quantum liquid or quantum droplet state. These so called quantum droplets may preserve their form in absence of external confinement because of quantum effects. The joint team of experimental physicists from Innsbruck and theoretical physicists from Hannover report on their findings in the journal Physical Review X.
“Our Quantum droplets are in the gas phase but they still drop like a rock,” explains experimental physicist Francesca Ferlaino when talking about the...
16.11.2016 | Event News
01.11.2016 | Event News
14.10.2016 | Event News
09.12.2016 | Life Sciences
09.12.2016 | Ecology, The Environment and Conservation
09.12.2016 | Health and Medicine