On the formation of the formate anion: Insights from population analyses

► We examine the formation pathway of the formate anion theoretically. ► The stationary points are characterized with highly accurate CCSD(T) calculations. ► Atomic charges and bond orders are analyzed along the reaction coordinate. ► The change from single and double CO-bonds to a delocalized state can be monitored. ► The bond forming starts at the point where the charge of OH− propagates to CO.