This work investigates the effects of the excluded volume and especially those of the chain stiffness on the structural and dynamical properties of a model polymer chain. The theoretical framework is the same as in th...This work investigates the effects of the excluded volume and especially those of the chain stiffness on the structural and dynamical properties of a model polymer chain. The theoretical framework is the same as in the recent works by Steinhauser et al., where a Rouse approach is adopted. Our model differs in that our chains have a finite average bending angle. As in the works by Steinhauser et al., Langevin dynamic simulations were performed without hydrodynamic interactions. Whereas this doesn＇t impact the static properties we obtain, it also allows us to compare our results on dynamic properties to those predicted by Rouse theory, where hydrodynamic interactions are also neglected. Our results show that the structural properties are very sensitive to the chain stiffness, whereas the dynamic scaling laws remain the same as those by Rouse theory, with the prefactor depending on the persistence length.展开更多
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 obe...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.展开更多
基金financially supported by the National Natural Science Foundation of China(No.10572056)
文摘This work investigates the effects of the excluded volume and especially those of the chain stiffness on the structural and dynamical properties of a model polymer chain. The theoretical framework is the same as in the recent works by Steinhauser et al., where a Rouse approach is adopted. Our model differs in that our chains have a finite average bending angle. As in the works by Steinhauser et al., Langevin dynamic simulations were performed without hydrodynamic interactions. Whereas this doesn＇t impact the static properties we obtain, it also allows us to compare our results on dynamic properties to those predicted by Rouse theory, where hydrodynamic interactions are also neglected. Our results show that the structural properties are very sensitive to the chain stiffness, whereas the dynamic scaling laws remain the same as those by Rouse theory, with the prefactor depending on the persistence length.
基金supported by the National Natural Science Foundation of China(Nos.21790343,21574142,21174154)the National Key Research and Development Program of China(No.2016YFB1100800).
文摘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.
