Edwin Sibert of the University of Wisconsin, Madison, is supported by the Theoretical and Computational Chemistry Program to study energy flow in polyatomic molecules in both gas and liquid phases using combined classical and quantum techniques. The research will encompass dynamical events that include vibrational relaxation, proton transfer reactions, and vibrational predissociation in the condensed phase. The objective is to develop robust molecular models of these processes. The model results should be consistent with experimental observations, and are expected to serve as a guide for future experimentation. Mixtures of bromoform and deuterated bromoform will be investigated with the goal of mapping out how energy travels between molecules. As well, formic acid dimer, a prototypical example of double proton transfer, will be studied in the gas and liquid phases. Finally, vibrational predissociation in the condensed phase, and in particular predissociation of hydrogen bonded oligomers, will be investigated.
Recent advances in an ultrafast laser spectroscopies enable chemists to probe the unfolding of molecular events with unprecedented time and size resolution. When these experiments are combined with thoughtful theoretical modeling from an atomistic perspective, significant insights are attained on how energy flow is controlled by forces between atoms. This research will make progress toward quantifying these ideas and developing predictive models for the events that occur as a result of these forces. Such models are essential, in the long term, for successful modeling of atmospheric, combustion, and biological processes at a molecular level.
