Modulation of the Product Upon the Reaction of CO With Dimethylamine Cluster: A Topological Analysis of the Reaction Mechanism.

The capture, activation, and reaction of carbon dioxide with dimethylamine (DMA) clusters have been investigated theoretically in the gas phase. The electronic structure of various compounds has been obtained using the density functional theory approach. The partitioning of the reaction path into different domains of structural stability has been done within the framework of the electron localization function (ELF) analysis. It has been found that DMA cluster size is a key parameter in modulating CO conversion, both energetically and structurally. It has been shown that as the size of DMA clusters increases, hidden domains transform into real domains and the energy barrier for the rate-limiting step significantly decreases, so that a slow and unlikely reaction becomes an instantaneous and viable reaction. Carbamic acid hydrogen bonded with a DMA dimer is the unique product of the reaction of CO with a DMA trimer.