Interactions of CO2 Anion Radicals with Electrolyte Environments from First-Principles Simulations

Abstract

Successful transformation of carbon dioxide (CO₂) into value-added products is of great interest, as it contributes in part to the circular carbon economy. Understanding chemical interactions that stabilize crucial reaction intermediates of CO₂ is important, and in this contribution, we employ atom centered density matrix propagation (ADMP) molecular dynamics simulations to investigate interactions between CO₂ ^- anion radicals with surrounding solvent molecules and electrolyte cations in both aqueous and nonaqueous environments. We show how different cations and solvents affect the stability of the CO₂ ^- anion radical by examining its angle and distance to a coordinating cation in molecular dynamics simulations. We identify that the strength of CO₂ ^- interactions can be tailored through choosing an appropriate cation and solvent combination. We anticipate that this fundamental understanding of cation/solvent interactions can facilitate the optimization of a chemical pathway that results from selective stabilization of a crucial reaction intermediate.