Lithium manganese oxide (LiMn O ) is a principal cathode material for high power and high energy density electrochemical storage on account of its low cost, non-toxicity, and ease of preparation relative to other cathode materials. However, there are well-documented problems with capacity fade of lithium ion batteries containing LiMn O . Experimental observations indicate that the manganese content of the electrolyte increases as an electrochemical cell containing LiMn O ages, suggesting that active material loss by dissolution of divalent manganese from the LiMn O surface is the primary reason for reduced cell life in LiMn O batteries. To improve the retention of manganese in the active material, it is key to understand the reactions that occur at the cathode surface. Although a thin layer of electrolyte decomposition products is known to form at the cathode surface, the speciation and reaction mechanisms of Mn in this interface layer are not yet well understood. To bridge this knowledge gap, reactive force field (ReaxFF) based molecular dynamics was applied to investigate the reactions occurring at the LiMn O cathode surface and the mechanisms that lead to manganese dissolution. The ReaxFFMD simulations reveal that the cathode-electrolyte interface layer is composed of oxidation products of electrolyte solvent molecules including aldehydes, esters, alcohols, polycarbonates, and organic radicals. The oxidation reaction pathways for the electrolyte solvent molecules involve the formation of surface hydroxyl species that react with exposed manganese atoms on the cathode surface. The presence of hydrogen fluoride (HF) induces formation of inorganic metal fluorides and surface hydroxyl species. Reaction products predicted by ReaxFF-based MD are in agreement with experimentally identified cathode-electrolyte interface compounds. An overall cathode-electrolyte interface reaction scheme is proposed based on the molecular simulation results.