Chain architecture effect on static and dynamic properties of unentangled polymers is explored by molecular dynamics simulation and Rouse mode analysis based on graph theory. For open chains, although they generally obey ideal scaling in chain dimensions, local structure exhibits nonideal behavior due to the incomplete excluded volume (EV) screening, the reduced mean square internal distance (MSID) can be well described by Wittmer’ theory for linear chains and the resulting chain swelling is architecture dependent, i.e., the more branches a bit stronger swelling. For rings, unlike open chains they are compact in term of global sizes. Due to EV effect and nonconcatenated constraints their local structure exhibits a quite different non-Gaussian behavior from open chains, i.e., reduced MSID curves do not collapse to a single master curve and fail to converge to a chain-length-independent constant, which makes the direct application of Wittmer’s theory to rings quite questionable. Deviation from ideality is further evidenced by limited applicability of Rouse prediction to mode amplitude and relaxation time at high modes as well as the non-constant and mode-dependent scaled Rouse mode amplitudes, while the latter is architecture-dependent and even molecular weight dependent for rings. The chain relaxation time is architecture-dependent, but the same scaling dependence on chain dimensions does hold for all studied architectures. Despite mode orthogonality at static state, the role of cross-correlation in orientation relaxation increases with time and the time-dependent coupling parameter rises faster for rings than open chains even at short time scales it is lower for rings.

通过分子动力学模拟和基于图论的Rouse模式分析，探讨链结构对未缠结聚合物静态和动态性质的影响。对于开放链，尽管它们通常遵循链尺寸的理想缩放比例，但由于不完全排除体积（EV）筛选，局部结构表现出不理想的行为，减小的均方根内部距离（MSID）可以由Wittmer线性链理论很好地描述并且结果链膨胀取决于体系结构，即，分支越多，膨胀就越强。对于开环，与开放链不同，它们在整体尺寸方面很紧凑。由于EV效应和非串联约束，它们的局部结构表现出与开放链完全不同的非高斯行为，即，简化后的MSID曲线不会折叠成一条主曲线，也不会收敛到与链长无关的常数，这使得将Wittmer的理论直接应用于环非常令人怀疑。Rouse预测对高模态下的振幅和弛豫时间的适用性有限，以及非恒定且依赖于模式的成比例的Rouse模态振幅进一步证明了与理想性的偏离，而后者取决于体系结构，甚至取决于分子量戒指。链松弛时间取决于体系结构，但是对于所有研究的体系结构，链规模的比例缩放依旧相同。尽管在静态下模式正交，