Potential Energy Surface for Anaerobic Oxidation of Methane via Fumarate Addition

Abstract

Microbially mediated anaerobic oxidation of methane (AOM) is an important sink in the global methane cycle, but the mechanism and microorganisms responsible for this oxidation are not fully known. Using quantum chemical calculations, fumarate addition to methane was examined to determine if it could be an energetically feasible mechanism for AOM. A potential energy surface (PES) for the initial reaction was created and the results suggest the reaction is exothermic, with a calculated overall energy change between -9.8 and -11.2 kcal/mol. The addition of methane to fumarate is calculated to be the highest point on the surface, 25.0-25.3 kcal/mol above the reactants. Of the three possible molecular configurations of fumarate considered, the one that presents the least steric obstacles to the addition reaction with methane yields the greatest energy gain. While 11.2 kcal/mol may support growth under energy limited conditions it is unknown if enzymes can mediate an energetic barrier of 25 kcal/mol. These calculated energies provide values for what could be one of the least reactive substrates to undergo fumarate addition, making methane a model substrate in defining the limits of energy barriers and minimal energy requirements for growth in reactions activated by glycyl radical-containing enzymes.