How to search for and reveal a hidden intermediate? The ELF topological description of non-synchronicity in double proton transfer reactions under oriented external electric field.

Context: The nature of double intermolecular proton transfer was studied with the ELF topological approach in two model dimers (the formic acid homodimer and the 1,2,3-triazole-guanidine heterodimer) under an oriented external electric field. It has been shown that each of the two dimers can have either a one-step (one transition state structure) or two-step (two transition state structures) reaction path, depending on the intensity and orientation of the external electric field. The presence of a singularly broad shoulder (plateau in the case of homodimer and plateau-like for heterodimer) around the formal transition state structure results from the strong asynchronicity of the reaction.

Influence of an Oriented External Electric Field on the Mechanism of Double Proton Transfer between Pyrazole and Guanidine: from an Asynchronous Plateau Transition State to a Synchronous or Stepwise Mechanism.

The double proton transfer (DPT) reaction between pyrazole and guanidine, a concerted reaction but strongly asynchronous and presenting a "plateau transition region", has been theoretically reinvestigated in the presence of an external uniform electric field. First, we computed the reaction path by DFT and proposed a very detailed description of the constitutive electronic events, based on the ELF topology and the bond evolution theory. Then, we studied the effect of an oriented external electric field (OEEF) on the reaction mechanism, for an OEEF oriented along the proton transfer axis.