Abstract
This study compares molecular calculations performed with molecular and periodic codes through an investigation of the solvation structures of alkali and alkaline earth metal ions in tetraglyme solution. The two codes are able to produce equivalent structural and energetic information at the same level of theory, and in the presence of the implicit solvation model or not. This comparison reveals that molecular optimisations can be performed with periodic codes and used directly as input models for interface or electrochemistry calculations in order to preserve the solvent−solute interaction and the cavitation energy. By a rigorous comparison, we have demonstrated that equivalent energetic values can be obtained with the conventional PBE-D3 and the newly developed SCAN-rVV10 functional. Nevertheless, when the vibrational features are concerned and when the molecule possesses a highly conjugated system, the SCAN-rVV10 functional is required to describe the vibrational modes properly. The computed IR/Raman spectra can thus be used as essential information to determine the first solvation shell of metal ions in glyme-based solutions. In tetraglyme solution, the alkali and alkaline earth metal ions exhibit a diverse solvation structure. Small ions like Li+ and Mg2+ tend to adopt a coordination number of five or six, while larger ions, Na+, K+, and Ca2+, prefer an eight-coordinated environment, and the metal−ligand interaction increases in the order K+−O < Na+−O < Li+−O < Ca2+−O < Mg2+−O. The solvation spheres play a significant role in the stability and the reactivity of the solvated ions, and can thus be used as input models to construct the solvation structure in more sophisticated electrolytes, such as polyethylene oxide, or perform electrochemical calculations.