2008/07/01 by Ruchi Sharma, Charusita Chakravarty, E. Milotti · 1 citation
Chemical Engineering · Chemistry · Physics and Astronomy · #Molecular spectroscopy and chirality #Spectroscopy and Quantum Chemical Studies #Thermodynamic properties of mixtures #cond-mat.soft
paper · pdf · doi:10.1021/jp802085v
published as Journal of Physical Chemistry B, 112, 9071-9078, 2008 · 30 pages, 10 figures
openalex publication_date 2008/07/01 · arxiv created 2008/11/11 · arxiv updated 2009/12/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
Canonical ensemble molecular dynamics simulations of liquid methanol, modeled using a rigid-body, pair-additive potential, are used to compute static distributions and temporal correlations of tagged molecule potential energies as a means of characterizing the liquid state dynamics. The static distribution of tagged molecule potential energies shows a clear multimodal structure with three distinct peaks, similar to those observed previously in water and liquid silica. The multimodality is shown to originate from electrostatic effects, but not from local, hydrogen bond interactions. An interesting outcome of this study is the remarkable similarity in the tagged potential energy power spectra of methanol, water, and silica, despite the differences in the underlying interactions and the dimensionality of the network. All three liquids show a distinct multiple time scale (MTS) regime with a 1/ f (alpha) dependence with a clear positive correlation between the scaling exponent alpha and the diffusivity. The low-frequency limit of the MTS regime is determined by the frequency of crossover to white noise behavior which occurs at approximately 0.1 cm (-1) in the case of methanol under standard temperature and pressure conditions. The power spectral regime above 200 cm (-1) in all three systems is dominated by resonances due to localized vibrations, such as librations. The correlation between alpha and the diffusivity in all three liquids appears to be related to the strength of the coupling between the localized motions and the larger length/time scale network reorganizations. Thus, the time scales associated with network reorganization dynamics appear to be qualitatively similar in these systems, despite the fact that water and silica both display diffusional anomalies but methanol does not.