Polarizability in ionic liquid simulations causes hidden breakdown of linear response theory

Abstract

The validity of linear response theory (LRT) in computer simulations of solvation dynamics, i.e. the time-dependent Stokes shift, has been debated widely during the last decades. Since the use of LRT is computationally less expensive than the calculation of the true nonequilibrium response, it is often invoked for large systems exhibiting a particularly slow solvation response, e.g. ionic liquids. In the case of ionic liquids, LRT does not only need to capture the correct overall dynamics of the system, but also the contributions and timescales of the respective cation and anion movement. We show by large scale computer simulations that the contribution of the permanent dipoles to the solvation response obeys LRT to some extent, whereas the induced contributions in polarizable simulations lead to a failure of LRT for the respective ion contributions.