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An Analog Macroscopic Technique for Studying Molecular Hydrodynamic Processes in Dense Gases and Liquids

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Multiple time scale behaviors and network dynamics in liquid methanol.

Ruchi Sharma¹, Charusita Chakravarty, Edoardo Milotti

¹Department of Chemistry, Indian Institute of Technology-Delhi, New Delhi 110016, India.

The Journal of Physical Chemistry. B

|July 2, 2008

Summary

Molecular dynamics simulations reveal that liquid methanol exhibits a multimodal potential energy distribution, similar to water and silica. This structure, driven by electrostatic forces, shows universal scaling behavior in its dynamics, linking liquid network reorganization to diffusivity.

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Area of Science:

Physical Chemistry
Computational Chemistry
Materials Science

Background:

Understanding liquid state dynamics is crucial for various chemical and physical processes.
Previous studies on water and silica revealed multimodal potential energy distributions.
The role of electrostatic and hydrogen bonding interactions in liquid dynamics requires further investigation.

Purpose of the Study:

To characterize the liquid state dynamics of methanol using molecular dynamics simulations.
To investigate the origins of the multimodal structure in tagged molecule potential energies.
To compare the dynamic properties of methanol with those of water and liquid silica.

Main Methods:

Canonical ensemble molecular dynamics simulations of liquid methanol.
Modeling methanol using a rigid-body, pair-additive potential.
Computation of static distributions and temporal correlations of tagged molecule potential energies.

Main Results:

The static potential energy distribution of methanol exhibits a clear multimodal structure with three distinct peaks.
This multimodality originates from electrostatic effects, not hydrogen bonds.
Methanol, water, and silica share similar tagged potential energy power spectra, including a multiple time scale (MTS) regime with 1/f^(alpha) dependence and a positive correlation between alpha and diffusivity.

Conclusions:

The dynamic time scales of network reorganization are qualitatively similar across methanol, water, and silica.
The correlation between the scaling exponent alpha and diffusivity suggests a universal mechanism in liquid dynamics.
Despite differences in diffusional anomalies, the underlying network reorganization dynamics show remarkable similarities.