Molecular Dynamics of Chemical Reactions in Solution

Abstract

We hope to answer one of the most fundamental and important unsolved questions in chemistry: how, from a molecular perspective, do chemical reactions in solution actually occur. The key to solving this long-standing problem is to understand the molecular dynamics, i.e., the motions of the atoms and the forces that drive them. We have already developed theoretical techniques and computational procedures involving specialized computer hardware needed to calculate the molecular dynamics for many chemical reactions in solution. From the dynamics we have derived the interface for experimental verification, namely transient electronic, infrared, and Raman spectra as well as X-ray diffraction, all of which are potentially observable manifestations of the atomic motions during the reaction. We have tested our approach on the simple inorganic I2 photodissociation and solvent caging reaction. The agreement between molecular dynamics based theory and experimental picosecond transient electronic absorption spectrum as a function of solvent, time, and wavelength is sufficiently close as to indicate that for the first time we are discovering at least part of the molecular dynamics by which a real solution chemical reaction takes place.