First-Principles Calculations of Fischer-Tropsch Processes Catalyzed by Nitrogenase Enzymes.

CC coupling: The free energies of the CO and CN− reduction pathways are calculated to identify the routes favored by FeMoco and FeVco nitrogenase active sites. The potential‐limiting step in CO reduction is the initial protonation and adsorption of CHO*. CN− reduction is limited by a second protonation of HCN. Higher‐order hydrocarbons, limited by the same steps, are likely built from CH2* intermediates common to both CO and CN− reduction pathways. [ABSTRACT FROM AUTHOR]