Revisiting the question of what instantaneous normal modes tell us about liquid dynamics
The lack of a well-defined equilibrium reference configuration has long hindered a comprehensive atomic-level understanding of liquid dynamics and properties. The Instantaneous Normal Mode (INM) approach, which involves diagonalizing the Hessian matrix of potential energy in instantaneous liquid configurations, has emerged as a promising framework in this direction. However, several conceptual challenges remain, particularly related to the approach's inability to capture anharmonic effects. In this study, we present a set of "experimental facts" through a comprehensive INM analysis of simulated systems, including Ar, Xe, N2, CS2, Ga, and Pb, across a wide temperature range from the solid to gas phase. First, we examine the INM density of states (DOS) and compare it to the DOS obtained from the velocity auto-correlation function. We then analyze the temperature dependence of the fraction of unstable modes and the low-frequency slope of the INM DOS in search of potential universal behaviors. Furthermore, we explore the relationship between INMs and other properties of liquids, including the liquid-like to gas-like dynamical crossover and the momentum gap of collective shear waves. In addition, we investigate the INM spectrum at low temperatures as the system approaches the solid phase, revealing a significant fraction of unstable modes even in crystalline solids. Finally, we confirm the existence of a recently discussed cusp-like singularity in the INM eigenvalue spectrum and uncover its complex temperature-dependent behavior, challenging current theoretical models.
Authors
- Matteo Baggioli (ORCID: https://orcid.org/0000-0001-9392-7507)
- Xue Fan (ORCID: https://orcid.org/0000-0001-5943-6042)
- Sha Jin (ORCID: https://orcid.org/0000-0003-3398-9727)
Institutions
- Shanghai University (CN)
- Shanghai Jiao Tong University (CN)
- Shanghai Research Institute of Materials (CN)
- Shanghai Dianji University (CN)
Publication Details
- Journal
- The Journal of Chemical Physics
- Published
- 2025-03-18
- DOI
- https://doi.org/10.1063/5.0239061
- Citations
- 1
- Primary Topic
- Spectroscopy and Quantum Chemical Studies
- Type
- article
- Field-Weighted Citation Impact
- 1.25