Conspectus The concept of pericyclic reactions and the explanation of their specificity
through orbital symmetries introduced a new way of understanding reactions and looking for …

An entropic intermediate is defined as a free energy minimum that is not a potential energy
minimum; the favorable entropy in this region of the potential surface is responsible for the …

The calculation of accurate reaction energies and barrier heights is essential in
computational studies of reaction mechanisms and thermochemistry. To assess methods …

Modeling dynamical effects in chemical reactions typically requires ab initio molecular
dynamics (AIMD) simulations due to the breakdown of transition state theory (TST). Reactive …

Compared with the conventional Diels–Alder reaction, the development of selective cross-
Diels–Alder reactions between two different conjugated dienes, especially in a catalytic …

An ambimodal transition state (TS) that leads to formation of four different pericyclic reaction
products ([4+ 6]-,[2+ 8]-,[8+ 2]-, and [6+ 4]-cycloadducts) without any intervening minima has …

Many organic reactions are characterized by a complex mechanism with a variety of
transition states and intermediates of different chemical natures. Their correct and accurate …

The observation of post-transition-state dynamic effects in the context of metal-based
transformation is rare. To date, there has been no reported case of a dynamic effect for the …

Theoretical characterization of reactions of complex molecules depends on providing
consistent accuracy for the relative energies of intermediates and transition states. Here we …

The thermal dimerization of cycloheptatriene is predicted to occur by a concerted [6+ 4]
cycloaddition via an ambimodal [6+ 4]/[4+ 6] transition state (TS) and a competing stepwise …