Density functional theory for molecular orientation of hard rod fluids in hard slits

作者：Cao Da Peng^*; Cheng Li Sheng; Wang Wen Chuan

来源：Chinese Physics, 2007, 16(8): 2296-2303.

• density functional theory
• rodlike chain
• molecular orientation
• flexible chain

A density functional theory (DFT) is used to investigate molecular orientation of hard rod fluids in a hard slit. The DFT approach combines a modified fundamental measure theory (MFMT) for excluded-volume effect with the first order thermodynamics perturbation theory for chain connectivity. In the DFT approach, the intra-molecular bonding orientation function is introduced. We consider the effects of molecular length (i.e. aspect ratio of rod) and packing fraction on the orientations of hard rod fluids and flexible chains. For the flexible chains, the chain length has no significant effect while the packing fraction shows slight effect on the molecular orientation distribution. In contrast, for the hard rod fluids, the chain length determines the molecular orientation distribution, while the packing fraction has no significant effect on the molecular orientation distribution. By making a comparison between molecular orientations of the flexible chain and the hard rod fluid, we find that the molecular stiffness distinctly affects the molecular orientation. In addition, partitioning coefficient indicates that the longer rodlike molecule is more difficult to enter the confined phase, especially at low bulk packing fractions.

• 出版日期2007-8
• 单位北京化工大学