Liao Yi, Miao Bing
College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China.
J Chem Phys. 2015 Apr 28;142(16):164903. doi: 10.1063/1.4919305.
We study the structure factor of a single Gaussian chain confined between two macroscopic parallel plates theoretically. The chain propagator is constructed in terms of the eigen-spectrum of the Laplace operator under the Dirichlet boundary condition enforced at the two plates, by which the confinement effect enters the treatment through size-dependent eigen-spectrum. In terms of the series expansion solution for the chain propagator, we first calculate the confinement free energy and the confinement force for an arbitrary confinement strength. It is found that the confinement force scales to the distance between the two confining surfaces with a power of -3 for strong confinements and of -2 for weak confinements. Based on the ground state dominance approximation for strong confinements and the Euler-Maclaurin formula for weak confinements, we develop approximation theories for the two limit situations, which agree with the numerical results well. We further calculate the structure factor of the confined Gaussian chain in this slit geometry. While the scattering function of the transverse chain fluctuations perpendicular to the confinement direction is still a Debye function form, the structure factor for the longitudinal fluctuations along the confinement dimension starts with the monotonic Debye function behavior for weak confinements and develops a decaying oscillation behavior with the increase of confinements. The numerical results for the structure factor are also interpreted by developing approximation theories in different confinement regimes. Finally, the orientational average of the anisotropic structure factor is performed and an analytic expression for the averaged structure factor is derived under the ground state dominance approximation for strong confinements.
我们从理论上研究了限制在两个宏观平行板之间的单个高斯链的结构因子。通过在两个平板处施加狄利克雷边界条件下的拉普拉斯算子的本征谱来构建链传播子,由此限制效应通过与尺寸相关的本征谱进入处理过程。根据链传播子的级数展开解,我们首先计算了任意限制强度下的限制自由能和限制力。结果发现,对于强限制,限制力与两个限制表面之间的距离的幂次为 -3,对于弱限制则为 -2。基于强限制下的基态主导近似和弱限制下的欧拉 - 麦克劳林公式,我们针对这两种极限情况发展了近似理论,这些理论与数值结果吻合良好。我们进一步计算了这种狭缝几何结构中受限高斯链的结构因子。虽然垂直于限制方向的横向链涨落的散射函数仍然是德拜函数形式,但沿限制维度的纵向涨落的结构因子在弱限制时从单调的德拜函数行为开始,并随着限制的增加发展出衰减振荡行为。结构因子的数值结果也通过在不同限制区域发展近似理论来解释。最后,对各向异性结构因子进行取向平均,并在强限制的基态主导近似下推导出平均结构因子的解析表达式。