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

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.