Interaction between experiments, analytical theories and computation

PHYS 149

Rudolph A. Marcus, ram@caltech.edu, Divsion of Chemistry and Chemical Engineering, California Institute of Technology, Noyes Laboratory of Chemical Physics, 1200 E. California Blvd. MC 127-72, Pasadena, CA 91125-0072
Much of earlier theoretical chemistry involves equations and their application to experiments, Debye, Debye-Huckel, Kramers, TST, RRKM, for example. Sometimes one can use theory to relate different experiments without using adjustable parameters, in addition to predictions, as in electron transfers. A focus more recently is on computations for individual systems, permitting the treatment of specific data in a detailed fashion not hitherto possible. Computations also served as numerical experiments yielding new insights, vibrational adiabaticity, for example. Some recent formulations of theory in the analytic/computational domain in our group will be described, selected from the mass-independent isotope effect in ozone formation, catalysis of organic on-water reactions, intermittently fluorescent nanoparticles, temperature independence of the kinetic isotope effect for certain enzymes, and an abnormal pre-exponential factor below an enzyme “break-point” temperature. It will be interesting to see how the interaction between experiment, concepts, analytic theory, and computation will fare in the future.