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Issue 20, 2011
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Substitutional and orientational disorder in organic crystals: a symmetry-adapted ensemble model

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Abstract

Modelling of disorder in organic crystals is highly desirable since it would allow thermodynamic stabilities and other disorder-sensitive properties to be estimated for such systems. Two disordered organic molecular systems are modeled using a symmetry-adapted ensemble approach, in which the disordered system is treated as an ensemble of the configurations of a supercell with respect to substitution of one disorder component for another. Computation time is kept manageable by performing calculations only on the symmetrically inequivalent configurations. Calculations are presented on a substitutionally disordered system, the dichloro/dibromobenzene solid solution, and on an orientationally disordered system, eniluracil, and the resultant free energies, disorder patterns, and system properties are discussed. The results are found to be in agreement with experiment, when some physically implausible configurations are removed from the ensemble average for eniluracil, highlighting the dangers of a completely automated approach to organic crystal thermodynamics which ignores the barriers to equilibration once the crystal has been formed.

Graphical abstract: Substitutional and orientational disorder in organic crystals: a symmetry-adapted ensemble model

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Publication details

The article was received on 28 Jan 2011, accepted on 25 Mar 2011 and first published on 15 Apr 2011


Article type: Paper
DOI: 10.1039/C1CP20249A
Citation: Phys. Chem. Chem. Phys., 2011,13, 9590-9600
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    Substitutional and orientational disorder in organic crystals: a symmetry-adapted ensemble model

    M. Habgood, R. Grau-Crespo and S. L. Price, Phys. Chem. Chem. Phys., 2011, 13, 9590
    DOI: 10.1039/C1CP20249A

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