- 2018 American Chemical Society. Using reactive molecular dynamics simulations, we evaluate atomistic-level interactions leading to the formation of surface films on a Li-metal (100) surface in contact with an electrolyte solution. We observe the evolution of the interfacial region and the formation of well-defined regions with varying density and oxidation state of Li; the penetration of electrolyte molecules and in some cases their electron transfer-driven decomposition leading to the initial formation of solid electrolyte interphase products. The simulations are done in the absence of a bias potential and using various electrolyte compositions including highly reactive solvents such as ethylene carbonate and less reactive solvents such as 1,3-dioxolane mixed with a 1 M concentration of a lithium salt. The structure and oxidation state of Li and some of the fragments are followed through the metal dissolution process. The results are important to understand the nature of the Li-metal anode/electrolyte interface at open-circuit potential.