n-Heptane under pressure: structure and dynamics from molecular simulations

Krishnan, M. ; Balasubramanian, Sundaram (2004) n-Heptane under pressure: structure and dynamics from molecular simulations The Journal of Physical Chemistry B, 109 (5). pp. 1936-1946. ISSN 1089-5647

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Official URL: http://pubs.acs.org/doi/abs/10.1021/jp046889d

Related URL: http://dx.doi.org/10.1021/jp046889d


Atomistic molecular dynamics simulations have been performed in the isothermal-isobaric ensemble to explore the phase behavior of n-heptane. Motivated by recent high-pressure spectroscopic experiments on n-heptane, the present work aims at understanding the liquid-solid and the alluded to solid-solid transitions upon increasing pressure. Starting from the stabilized solid phase at 300 K and 10 kbar, we have investigated the range of these two transitions by a gradual decrease and increase of pressure, respectively. Although the solid-liquid transition has clear signatures such as the formation of gauche defects along the molecular backbone, the present model does not show any sign of a first-order solid-solid transition at high pressures. However, interesting changes in the environment around methyl groups and in their dynamics are observed. These have been substantiated by calculations of the vibrational density of states obtained from a normal-mode analysis and from the simulation trajectory.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:79832
Deposited On:30 Jan 2012 04:48
Last Modified:30 Jan 2012 04:48

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