Elucidating the mechanism behind the infrared spectral features and dynamics observed in the carbonyl stretch region of organic carbonates interacting with lithium ions

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Ultrafast infrared spectroscopy has become a very important tool for studying the structure and ultrafast dynamics in solution. In particular, it has been recently applied to investigate the molecular interactions and motions of lithium salts in organic carbonates. However, there has been a discrepancy in the molecular interpretation of the spectral features and dynamics derived from these spectroscopies. Hence, the mechanism behind spectral features appearing in the carbonyl stretching region was further investigated using linear and nonlinear spectroscopic tools and the co-solvent dilution strategy. Lithium perchlorate in a binary mixture of dimethyl carbonate (DMC) and tetrahydrofuran was used as part of the dilution strategy to identify the changes of the spectral features with the number of carbonates in the first solvation shell since both solvents have similar interaction energetics with the lithium ion. Experiments showed that more than one carbonate is always participating in the lithium ion solvation structures, even at the low concentration of DMC. Moreover, temperature-dependent study revealed that the exchange of the solvent molecules coordinating the lithium ion is not thermally accessible at room temperature. Furthermore, time-resolved IR experiments confirmed the presence of vibrationally coupled carbonyl stretches among coordinated DMC molecules and demonstrated that this process is significantly altered by limiting the number of carbonate molecules in the lithium ion solvation shell. Overall, the presented experimental findings strongly support the vibrational energy transfer as the mechanism behind the off-diagonal features appearing on the 2DIR spectra of solutions of lithium salt in organic carbonates.

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The Journal of chemical physics

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