Quantum Simulations of Hydrogen Bonding Effects in Glycerol Carbonate Electrolyte Solutions

The need for environmentally friendly nonaqueous solvents in electrochemistry and other fields has motivated recent research into the molecular-level solvation structure, thermodynamics, and dynamics of candidate organic liquids. In this paper, we present the results of quantum density functional theory simulations of glycerol carbonate (GC), a molecule that has been proposed as a solvent for green industrial chemistry, nonaqueous alternatives for biocatalytic reactions, and liquid media in energy storage devices. We investigate the structure and dynamics of both the pure GC liquid and electrolyte solutions containing KF and KCl ion pairs. These simulations reveal the importance of hydrogen bonding that controls the structural and dynamic behavior of the pure liquid and ion association in the electrolyte solutions. The results illustrate the difficulties associated with classical modeling of complex organic solvents. The simulations lead to a better understanding of the underlying mechanisms behind the previously observed peculiar ion-specific behavior in GC electrolyte solutions.