Understanding the vibrational density of states of liquids using instantaneous normal mode theory
arxiv(2023)
摘要
Liquid dynamics play crucial roles in chemical and physical processes,
ranging from biological systems to engineering applications. Yet, the
vibrational properties of liquids are poorly understood when compared to the
case of crystalline solids. Here, we report experimental neutron-scattering
measurements of the vibrational density of states (VDOS) of water and liquid
Fomblin in a wide range of temperatures. In the liquid phase, we observe a
universal low-energy linear scaling of the experimental VDOS as a function of
the frequency, which persists at all temperatures. The low-frequency scaling of
the VDOS exhibits a sharp jump at the melting point of water, below which the
standard Debye's law is recovered. On the contrary, in Fomblin, we observe a
continuous transition reflecting its glassy dynamics, which is confirmed by
structure measurements. More importantly, in both systems, we find that the
slope of this linear behavior grows with temperature following an exponential
Arrhenius-like form, as predicted by instantaneous normal mode (INM) theory.
The microscopic origin of this exponential behavior lies in the thermally
activated hopping across the energy barriers in the liquid potential landscape.
We confirm this experimental trend using molecular dynamics simulations and
show that the predictions of INM theory for the shape of the VDOS in the liquid
phase are in qualitative agreement with the experimental and simulation data.
On the other hand, from a more quantitative perspective, the predictions from
the normal modes analysis under-estimate the energy scale entering in the
exponential temperature behavior of the VDOS slope by a factor of ≈
2-3. Anharmonic effects, that are not entirely captured by the INM analysis,
are probably the origin of this discrepancy.
更多查看译文
AI 理解论文
溯源树
样例
生成溯源树,研究论文发展脉络
Chat Paper
正在生成论文摘要