Direct Correlation between Short-Range Vibrational Spectral Diffusion and Localized Ion-Cage Dynamics of...

The molecular dynamics simulations of a "water-in-salt" electrolyte, lithium bis(trifluoromethyl sulfonyl) imide (LiNTf₂), with a varying concentration range of 3 to 20 m were performed to establish a direct connection between a dynamic property like the ion-cage lifetime with the short-range vibrational stretching frequency shift of the used probe, HOD. The properties reported here are compared to that obtained from experiments performed at the same concentrations. The time-series wavelet transform was adopted as a preferable mathematical tool for calculating the instantaneous fluctuating frequencies of the probe O-D stretch mode and the concentration-dependent vibrational stretch spectral signature based on the variable functions associated with a particular chemical bond derived from classical molecular dynamics trajectories. The decay time constants of frequency fluctuations and the lifetime of the ion cage (τ_IC) were estimated as a function of salt concentration. Herein, we emphasize the correlation between the slowest time constant (τ₃) of the decay of O-D stretch frequency fluctuations and the timescales associated with the lifetime of ion cages (τ_IC). The results exhibit that the existing relationships were also concentration-dependent. Therefore, this study highlights the connection between the ionic motions that regulate the overall system dynamics with the short-range vibrational frequency shift of the used probe, which was used similar to experiments. It also provides an understanding of the interionic interactions and the dynamical and spectral properties of the electrolytic mixtures. We establish a direct correlation between short-range frequency profile and localized ion-cage lifetime, which can fill the gap of understanding between viscosity, vibrational frequency, and ion-cage dynamics of electrolytes.