A recent development in computational chemistry: chemical reactions from first principles molecular dynamics simulations.

First-principles molecular dynamics simulations have recently been found an effective tool to study a large variety of chemical problems. Finite temperature simulations reveal unique information, including explicit dynamical effects and the evaluation of proper free energy differences. Moreover, dynamics simulations reveal information on the flexibility of molecular systems, and elucidate, often otherwise inaccessible, mechanistic details of chemical reactions.

The kinetics of cyclization reactions on polyaromatics from first principles.

Ab initio density functional theory calculations are presented on cyclization reactions of polyaromatics involved in coke formation during the thermal cracking of hydrocarbons. During coke formation, cyclization can take place at various sites, differing from each other by the local polyaromatic structure. This local structure also determines the minimum number of carbon atoms that must be added to allow the formation of a new ring.

Ab initio and experimental study on thermally degradable polycarbonates: the effect of substituents on the reaction rates.

Thermal elimination reactions on polycarbonates are investigated from both theoretical and experimental points of view, to obtain insight into the microscopic aspects that influence the reaction mechanism and rates. In particular, attention is focused on the influence of the type of substituents in the polymer chain on the reaction rates. Ab initio density functional theory calculations are performed on a series of model compound systems for the polycarbonates under study, in particular carbonates differing by the groups attached at the alpha and beta carbon atoms.