This study elucidates the mechanistic study of the catalytic water oxidation process by an iron complex of cis-dichloro-1,4,8,11-tetra azacyclotetradecane (cis-[Fe(cyclam)Cl2]Cl) in the presence of explicit water molecules with the help of metadynamics method-based first-principles molecular dynamics simulations performed at 300 K and ambient pressure. We considered [FeV(cyclam)(O)2]+ and [FeV(cyclam)(OH)(O)]2+ as the active catalytic species in liquid water for the water oxidation process and calculated the free-energy landscapes of various steps involved in the mechanistic pathway. Our microkinetics study of the oxygen-oxygen bond formation by both the active catalytic species reveals that the transfer of proton to the cis-oxo or hydroxide of the active catalytic species is the rate-determining step, and the transfer of the hydroxide to the iron-oxo moiety is the less free energetic path. Overall, the O-O bond formation by the active catalytic species [FeV(cyclam)(OH)(O)]2+ is more favorable. We carried out a partial charge analysis of the atoms involved in the reaction. From the Lowdin and Mulliken charge analysis on the atoms, we confirm that the addition of a water molecule takes place as the nucleophile that leads to the formation of the peroxide complex. The superoxide complex is formed from the peroxide complex through the proton-coupled electron transfer process. The electron transfer was confirmed by the analysis of the projected density of states (PDOS) and the local density of states. We presented the energetics of crystal field splitting for the peroxide and superoxide complexes based on the PDOS. In the case of liberation of dioxygen with addition of the water molecule, microkinetics analysis reveals that the release of oxygen is a high free energetic step than the addition of water molecules. Overall, both steps involving the oxygen-oxygen bond formation and the release of oxygen molecules are possible in the case of [FeV(cyclam)(OH)(O)]2+ as the active catalytic species. These thermodynamic and kinetic aspects of the water oxidation process may help in developing new water oxidation catalysts. Copyright © 2019 American Chemical Society.