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Journal of Chemical Physics / Volume 134 / Issue 11 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation
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J. Chem. Phys. 134, 114501 (2011); http://dx.doi.org/10.1063/1.3559153 (6 pages)

Crystallization of the Lewis–Wahnström ortho-terphenyl model

Ulf R. Pedersen1, Toby S. Hudson2, and Peter Harrowell2

1Department of Chemistry, University of California, Berkeley, California 94720-1460, USA
2School of Chemistry, University of Sydney, Sydney NSW 2006, Australia

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(Received 8 November 2010; accepted 4 February 2011; published online 15 March 2011)

Crystallization is observed during microsecond long molecular dynamics simulations of bent trimers, a molecular model proposed by Lewis and Wahnström for ortho-terphenyl. In the crystal, the three spheres that make up the rigid molecule sit near sites of a body centered cubic lattice. The trimer bond angle is almost optimal for this structure. The crystal exhibits orientational disorder with the molecules aligned randomly along the three Cartesian axis, i.e., cubatic orientational order. The rotational and translational mobilities exhibit only modest decreases on crystallization, by factors of 10 and 3, respectively. The rotational relaxation does change from Debye-like in the liquid to large angle jumps in the crystal. We consider the origin of the superior glass forming ability of the trimer over the monatomic liquid.

© 2011 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. MODEL AND ALGORITHM
  3. RESULTS
    1. Spontaneous crystallization of the supercooled liquid
    2. Crystal structure
    3. Relaxation kinetics in the liquid and solid phases
  4. DISCUSSION

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KEYWORDS and PACS

Keywords

bond angles, crystallisation, molecular dynamics method, organic compounds, vitrification

PACS

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3559153

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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Figures (click on thumbnails to view enlargements)

FIG.1
Drop in potential energy due to crystallization of six independent runs at ρ = 1.135 g/ml and T = 375 K. Full lines are running averages shown for clarity. The average crystallization time at this density, temperature, and system size is estimated to tcryst = 2 × 10−6 s.

FIG.1 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.2
Crystal configuration formed spontaneously from the supercooled liquid at ρ = 1.135 g/ml and T = 375 K. The left box display positions of the Lennard-Jones centers (spheres), that are in a near-BCC lattice. Atoms in molecules are connected and molecules are given random colors for clarity. In the right box, only the line connecting the two outer atoms of the trimer are shown. We note the presence of considerable orientational disorder, constrained, however, to orientations that are either parallel or perpendicular to each other, i.e., cubatic order.

FIG.2 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.3
On the left, a trimer (indicated in red) with an optimal bond angle of 70.5° occupies the sites of a BCC lattice. On the right, the trimer with a bond angle and bond length similar to that of the LW trimer is arranged on a near-BCC lattice.

FIG.3 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.4
The unit cell of an orientationally ordered arrangement of red trimers. Black sites represent the rest of the lattice sites, which are occupied by periodic images of the trimer sites. This forms a herringbone structure on the (0math1) plane. Nearest-neighbor interactions of lengths r1 (blue long-dash), r2 (orange dotted) and r3 = a (black, gray, and magenta hashed) are marked. Note that this is an idealized structure missing some orientational freedom as discussed in the text.

FIG.4 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.5
Potential energy of the crystal as estimated by Eq. ( 1 ) as a function of the trimer angle φ. The shift function S use to truncate interactions smoothly only introduces a −72εγ ≃ 1.8 kJ/mol shift of the shown energies.

FIG.5 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.6
Distribution of the angles between the orientation vectors of neighbors in the crystal (as generated by simulation) and in the liquid. The green dashed line indicates a random distribution. Neighbor molecules are those contributing to the first peak of the radial distribution function.

FIG.6 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.7
The drop in potential energy (a) is accompanied by cubatic ordering (b). Green crosses indicates cubatic order parameter Qi’s (Eq. ( 2 )) and the black line the global cubatic order parameter Q (ρ = 1.135 g/ml, T = 375 K). Negative Qi’s in the crystalline phase are associated with orientational defects .

FIG.7 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.8
(a) Rotational autocorrelation functions defined as Cl(t) = 〈Pl{cos [θ(0)]}Pl{cos [θ(t)]}〉 where θ is the angle between the trimer base and either math, math or math and Pl is the Legendre polynomial of either rank l = 1 (+) or l = 2 (×). Cl(t)’s are evaluated for both the liquid (blue) and crystal (red) at ρ = 1.135 g/ml and T = 375 K. Rotational relaxation time is only affected by a factor of 10 on crystallizing. Solid lines (black) indicated fits to stretched exponentials. For the liquid state, we find C1 fit (t) = 0.99exp(−(t/1.9×10−8s)0.87) and C2 fit (t) = 1.00exp(−(t/8.7×10−9s)0.73) and for the crystalline state C1 fit (t) = 0.95exp(−(t/1.4×10−7s)0.67) and C2 fit (t) = 0.90exp(−(t/1.2×10−7s)0.60). (b) Distribution of angular displacements of molecular orientations after 1 ns.

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FIG.9
Mean squared displacement of LJ centers (full lines) and center of masses (dashed lines) in the crystal (red) and liquid (blue) phases at ρ = 1.135 g/ml and T = 375 K. Center of mass diffusion constants in liquid and crystal, estimated from long time displacements, are 1.6 × 10−12 and 5.3 × 10−13 m2/s, respectively.

FIG.9 Download High Resolution Image (.zip file) | Export Figure to PowerPoint


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