Shaul Mukamel is supported by a grant from the Theoretical and Computational Chemistry Program to continue his research in molecular relaxation and radiative processes. He will continue his development of theoretical methods for the design and systematic interpretation of multidimensional femtosecond correlation spectroscopies in systems of coupled localized vibrational or electronic chromophores. Visible and infrared analogues of multiple-pulse NMR techniques provide novel snapshot probes into the structure as well as dynamics, interactions and relaxation processes of complex molecular assemblies. The fundamental theoretical concepts underlying techniques involving molecular responses to sequences of shaped and timed radiation pulses will be developed. Semiclassical methods for simulating nonlinear response functions will be tested. A classical-oscillator description of the spectroscopies will be developed, setting the stage for designing new pulse sequences that accomplish the same goals as their NMR analogues and providing a framework for computing and interpreting multidimensional signals.
The advent of pulsed laser technology combined with the use of non-linear optical techniques has led to a large number of new methods to probe gas-phase and condensed-phase molecular systems. Mukamel is developing theoretical techniques that are central to the interpretation of the data obtained from these experiments. These interpretations lead to many important insights regarding chemical reactions and the effects of solvation in condensed phase systems that can have application to understanding biological systems.
