Modeling Alkylcopper Decomposition Pathway: Deciphering Pre-Nucleation Processes for Metallic Cu Nanoparticles...

This study investigates the thermal decomposition mechanism of ethylcopper through density functional theory (DFT) calculations, focusing on the pathways leading to the formation of ethane. We emphasize the importance of aggregation and Cu-Cu bond formation and evaluate the autocatalytic effect of Cu⁽⁰⁾ atoms in these mechanisms. The retained reactions pathways go through a ẞ-H elimination step exhibiting a relatively low activation barrier but resulting in metastable hydrido-copper complexes. It is followed by the reduction step itself which is found to be the rate determining step. Formation of trimers from the start or in the course of the reaction is found to play a major role in the thermal decomposition process of ethylcopper. Together, these insights are confronted to experimental data from the literature and provide a comprehensive understanding of the thermodynamic and kinetic aspect of these pre-nucleation processes.