Study of organic reactions using chemical reactivity descriptors derived through a temperature-dependent approach

Abstract

Using the ratio of two fluctuations in the temperature-dependent density functional theory, the local counterpart of a global response function and the linear (non-local) counterpart of a local response function can be constructed. Here, we analyze the local chemical potential, local hardness, Fukui kernel and dual descriptor kernel and test their performance for describing and interpreting reactivity features for a diverse set of organic chemical reactions, including acid–base reactions, aliphatic nucleophilic substitutions, aromatic electrophilic substitutions and Markovnikov additions. Despite important differences in size and functionalization between some substrates belonging to a given chemical reaction type, temperature-dependent chemical reactivity descriptors were able to reproduce experimental or computational trends in all cases. We identify relevant chemical interactions belonging to a particular family of reactions and the molecular moieties responsible for such interactions. In general, our results are consistent with traditional chemical interpretations. However, in some cases the information contained in the temperature-dependent chemical reactivity descriptors allows one to gain new insights about the organic chemistry reactions considered here.