Concurrent phenomena at the reaction path of the \(S_{\mathrm N}2\) reaction \(\mathrm{CH}_3\mathrm{Cl}+F^-\). Information planes and statistical complexity analysis (Q280609)

Summary: An information-theoretical complexity analysis of the \(S_{\mathrm N}2\) exchange reaction for \(\mathrm{CH}_3\mathrm{Cl}+F^-\) is performed in both position and momentum spaces by means of the following composite functionals of the one-particle density: \textit{D-L} and \textit{I-J} planes and Fisher-Shannon's (FS) and López-Ruiz-Mancini-Calbet (LMC) shape complexities. It was found that all the chemical concepts traditionally assigned to elementary reactions such as the breaking/forming regions (B-B/F), the charge transfer/reorganization and the charge repulsion can be unraveled from the phenomenological analysis performed in this study through aspects of localizability, uniformity and disorder associated with the information-theoretical functionals. In contrast, no energy-based functionals can reveal the above mentioned chemical concepts. In addition, it is found that the TS critical point for this reaction does not show any chemical meaning (other than the barrier height) as compared with the concurrent processes revealed by the information-theoretical analysis. Instead, it is apparent from this study that a maximum delocalized state could be identified in the transition region which is associated to the charge transfer process as a new concurrent phenomenon associated with the charge transfer region (CT) for the ion-complex is identified. Finally it is discussed why most of the chemical features of interest (e.g., CT, B-B/F) are only revealed when some information-theoretic properties are taken into account, such as localizability, uniformity and disorder.