1/f spectrum and memory function analysis of solvation dynamics in a room-temperature ionic liquid

To understand the non-exponential relaxation associated with solvation dynamics in the ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate, we study power spectra of the fluctuating Franck-Condon energy gap of a diatomic probe solute via molecular dynamics simulations. Results show 1/f dependence in a wide frequency range over 2 to 3 decades, indicating distributed relaxation times. We analyze the memory function and solvation time in the framework of the generalized Langevin equation using a simple model description for the power spectrum. It is found that the crossover frequency toward the white noise plateau is directly related to the time scale for the memory function and thus the solvation time. Specifically, the low crossover frequency observed in the ionic liquid leads to a slowly-decaying tail in its memory function and long solvation time. By contrast, acetonitrile characterized by a high crossover frequency and (near) absence of 1/f behavior in its power spectra shows fast relaxation of the memory function and single-exponential decay of solvation dynamics in the long-time regime.