Enhanced Mobility during Diels-Alder Reaction: Results of Molecular Simulations

Recent measurements indicate enhanced mobility of solvent molecules during Diels-Alder (DA) and other common chemical reactions. We present results of molecular dynamics simulations of the last stages of the DA cycloaddition reaction, from the transition state configuration to product, of furfurylamine and maleimide in acetonitrile at reactant concentrations studied experimentally. We find enhanced mobility of solvent and reactant molecules up to at least a nanometer from the DA product over hundreds of picoseconds. Local heating is ruled out as a factor in the enhanced mobility observed in the simulations, which is instead found to be due to solvent relaxation following the formation of the DA product.