title: Knots "Choke Off" Polymers upon Stretching.
abstract: Long polymer chains inevitably get tangled into knots. Like macroscopic ropes, polymer chains are substantially weakened by knots and the rupture point is always located at the "entry" or "exit" of the knot. However, these phenomena are only poorly understood at a molecular level. Here we show that when a knotted polyethylene chain is tightened, most of the stress energy is stored in torsions around the curved part of the chain. The torsions act as "work funnels" that effectively localize mechanical stress in the immediate vicinity of the knot. As a result, the knot "chokes" the chain at its entry or exit, thus leading to bond rupture at much lower forces than those needed to break a linear, unknotted chain. Our work not only explains the weakening of the polymer chain and the position of the rupture point, but more generally demonstrates that chemical bonds do not have to be extensively stretched to be broken.
authors.affiliation: Interdisziplinäres Zentrum für Wissenschaftliches Rechnen, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 368, 69120 Heidelberg (Germany).
authors.forename: Tim
authors.initials: T
authors.lastname: Stauch
authors.affiliation: Interdisziplinäres Zentrum für Wissenschaftliches Rechnen, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 368, 69120 Heidelberg (Germany). dreuw@uni-heidelberg.de.
authors.forename: Andreas
authors.initials: A
authors.lastname: Dreuw
keywords: ab initio calculations; computational chemistry; density functional calculations; mechanical properties; polymers