Revisiting the question of what instantaneous normal modes tell us about liquid dynamics

Abstract

The absence of a well-defined equilibrium reference configuration and the inevitable frequent atomic rearrangements have long obstructed the achievement of a complete atomic-level understanding of liquid dynamics and properties, a challenge that continues to be unresolved. The instantaneous normal mode (INM) approach, based on the diagonalization of the potential energy Hessian matrix in instantaneous liquid configurations, has been shown to be a promising starting point to predict thermodynamic and dynamical properties of liquids but presents several conceptual difficulties that remain to be addressed. More in general, due to the inability of capturing anharmonic effects, what INMs can tell us about liquid dynamics remains an open question. In this work, we provide a general set of ``experimental facts'' by performing a comprehensive INM analysis of several simulated systems, including Ar, Xe, N$_2$, CS$_2$, Ga and Pb, in a large range of temperatures from the solid to the gas phase. We first study the INM density of states (DOS) and compare it to the density of state function obtained from the velocity auto-correlation function. Secondly, we analyze the temperature dependence of the fraction of unstable modes and of the low-frequency slope of the INM DOS, in search of possible universal behaviors. We then explore the connection between INMs and other properties of liquids including the liquid-like to gas-like dynamical crossover and the momentum gap of collective shear waves. Moreover, we investigate the INM spectrum at low temperature upon approaching the solid phase, revealing the existence of a large fraction of unstable modes also in crystalline solids. Finally, we verify the existence of a recently discussed cusp-like singularity in the INM eigenvalue spectrum and reveal its complex behavior upon dialing temperature that challenges the existing theoretical models.