Supporting Information and Computational Data for Descriptor-Based Analysis of Ligand Competition in Lithium-Ion Carbonate Solvation

Descriptor-Based Analysis of Ligand Competition in Lithium-Ion Carbonate Solvation This dataset contains the computational data supporting the manuscript, "Descriptor-Based Analysis of Ligand Competition in Lithium-Ion Carbonate Solvation." The study investigates the thermodynamics, structure, and electronic properties of mixed ethylene carbonate (EC) and dimethyl carbonate (DMC) coordination complexes of Li+ using density functional theory (DFT) and continuum-solvated microsolvation models. The dataset includes optimized geometries, Gaussian input and output files, thermodynamic analyses, and Natural Bond Orbital (NBO) results for Li+(EC)4-n(DMC)n complexes (n = 0-4) and a corresponding outer-shell Li⁺(EC)3···DMC structure. The calculations were performed using the M06-2X functional with def2-SVP geometry optimizations, def2-TZVPP single-point energy refinements, and continuum solvation treatment using the SMD model. The results demonstrate that substitution of EC by DMC within the first coordination shell is generally near thermoneutral, indicating competitive coordination between the two carbonate solvents. In contrast, outer-shell DMC coordination is significantly less favorable, supporting a model in which direct carbonyl coordination is required for thermodynamic competitiveness. Structural and electronic analyses further show that Li⁺ maintains a four-coordinate inner-shell environment throughout the substitution sequence. Contents include: · Gaussian input files (.com) · Gaussian output files (.log/.out) · Optimized molecular geometries (.xyz) · Thermodynamic data tables · Relative and stepwise substitution free-energy analyses · Structural parameter tables · Natural Bond Orbital (NBO) analyses · Supporting information associated with the manuscript These files are provided to facilitate reproducibility, validation, and future investigations of lithium-ion solvation and ligand competition in carbonate-based battery electrolytes. Author: Bruce M. Prince Affiliation: Department of Chemistry, Texas Southern University, Houston, Texas, USA