The Influence of Vibrations on Reactions in Gases and Liquids (SCS)

Chemical reaction inherently involves the rearrangement of the connectivity of nuclei. Thus, vibrational excitation, which moves the nuclei relative to each other, is potentially a means of controlling the course of chemical reactions. Different experiments have clearly demonstrated this behavior in gas-phase reactions, and they raise the possibility of observing the same phenomena in a liquid, where frequent interactions complicate the situation.
 
There is a series of questions to ask about the role of vibrational energy in chemical reactions in solution: How fast does vibrational energy flow around a molecule in solution? Do the behavior of gas-phase reactions predict behavior in solution? How does the release of energy into products differ in solution from that in the gas phase? Can vibrational excitation accelerate a reaction in solution? A collection of experiments using ultrafast laser pulses begins to answer these questions, and studies of vibrationally excited molecules in solution provide the first evidence of vibrational excitation influencing a reaction in solution.