Transferability of Coarse-Grained Force Field for nCB Liquid Crystal Systems

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• 作者：Jianguo Zhang ; Hongxia Guo
• 刊名：Journal of Physical Chemistry B
• 出版年：2014
• 出版时间：May 1, 2014
• 年：2014
• 卷：118
• 期：17
• 页码：4647-4660
• 全文大小：509K
• 年卷期：v.118,no.17(May 1, 2014)
• ISSN：1520-5207

文摘

In this paper, the transferability of the coarse-grained (CG) force field originally developed for the liquid crystal (LC) molecule 5CB (Zhang et al. J. Phys. Chem. B 2012, 116, 2075鈭?089) was investigated by its homologues 6CB and 8CB molecules. Note that, to construct the 5CB CG force field, we combined the structure-based and thermodynamic quantities-based methods and at the same time attempted to use several fragment molecular systems to derive the CG nonbonded interaction parameters. The resultant 5CB CG force field exhibits a good transferability to some extent. For example, not only the experimental densities, the local packing of atom groups, and the antiparallel arrangements of nearest neighboring molecules, but also the unique LC mesophases as well as the nematic鈥搃sotropic phase transition temperatures of 6CB and 8CB were reproduced. Meanwhile, the limitations of this 5CB CG force field were also observed, such as the phase transition from nematic to smectic was postponed to the lower temperature and the resulting smectic phase structure is single-layer-like instead of partially interdigitated bilayer-like as observed in underlying atomistic model. Apparently, more attention should be paid when applying a CG force field to the state point which is quite different from which the force field is explicitly parametrized for. The origin of the above limitations can be potentially traced back to the inherent simplifications and some approximations often adopted in the creation process of CG force field, for example, choosing symmetric CG potentials which do not explicitly include electrostatic interactions and are parametrized by reproducing the target properties of the specific nematic 5CB phase at 300 K and 1 atm, as well as using soft nonbonded potential and excluding torsion barriers. Moreover, although by construction this CG force field could inevitably incorporate both thermodynamic and local structural information on the nematic 5CB phase, the anisotropic diffusion coefficient ratios for different LC phases in both 6CB and 8CB systems are reproduced well. All these findings suggest that the multiproperty parametrization route together with fragment-based method provides a new approach to maximize the possibility to simultaneously reproduce multiple physical properties of a given molecule or related molecules with similar chemical structures at other state points.