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Rudolph
A. Marcus
Arthur
Amos Noyes Professor of Chemistry
Research in the Marcus group involves analyses and theories of a wide range of phenomena in chemical kinetics and in related processes. Its primary focus is on formulating theories to explain new and often unexpected experimental results, as well as improving the understanding of earlier work. We explore the relation between phenomena in different fields.
Recent examples include the striking “on-water“ catalysis of organic reactions and the fluorescent intermittency of semiconductor nanoparticles (quantum dots). Another line of our activities relates to enzyme catalysis. It involves formulating relations between single molecule fluctuations of different properties of enzymes, such as catalytic activity, radiative lifetime and spectral diffusion of chromophores. In this relation the electrostatic fluctuations provide a guideline. Further topics address other characteristics of enzyme catalysis under natural conditions, such as the temperature independent H/D kinetic isotope effect. The abnormal Arrhenius pre-exponential factor in the catalytic rate of a thermophilic enzyme operating at temperatures below its “break-point” is also analyzed.
Our recent gas phase studies address the mass-independent isotopic fractionation in the formation of ozone and other stratospheric gases, and include the fractionation in the earliest solids in the solar system. The role of isotopic fractionation is also explored in atmospheric processes such as the photolysis of the greenhouse gas N2O and the CO + OH reaction.
Much of this research is related to both understanding puzzling phenomena and to making predictions for further experiments. The tools utilize both analytical and computational methods.
