Trends in the Reactivity of Pentacyclic Ether Derivatives on Silicon and Germanium Surfaces Revealed by Energy Decomposition Analysis for Extended Systems

We analyze the adsorption and ring‐opening reaction of pentacyclic chalcogen alkyls with chalcogen atoms ranging from oxygen to tellurium using computational analysis. Thus extends our previous investigation of THF on silicon towards germanium surface and towards the heavier chalcogen homologues. We found an increasing dative bond strength of the precursor state with the period of the chalcogen atom on both surfaces. Using energy decomposition analysis for extended systems (pEDA), differences in the trends between silicon and germanium were revealed. Following the dative bound state, subsequent ring‐opening reactions were found to proceed via a nucleophilic back‐side attack, similar to a molecular SN2 reaction. Reaction energies and barrier heights show a maximum for the sulfur derivative. This trend was found to correlate with the position of the transition state in the reaction and agrees with the molecular reactivity. The uniquely low barrier of THF can be attributed to its ring strain. Our findings shed light on the fundamental aspects of surface chemistry and the benefits of using quantitative bonding analysis in this field. It also paves the way for future explorations into the functionalization of semiconductor surfaces using higher‐period ether derivatives.