Interaction between experiments, analytical theories and computation

PHYS 149

Rudolph A. Marcus,, 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.