Self-organization and the formation of helicoidal polymer structures

Melker, Alexander I.; Воробьева, Т. В.

doi:10.1134/1.1129889

Cited by 3 publications

(2 citation statements)

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“…The dissociation of a 1-D chain subject to constant tensile force is a problem in unimolecular kinetics, and a fundamental issue in unimolecular kinetics concerns the applicability of statistical approaches such as RRKM [47][48][49][50][51] or transition state theory [52][53][54][55][56][57]. Previous theoretical work has suggested that dissociation of atomic chains under stress is not amenable to simple statistical approaches [40,[58][59][60][61][62][63][64][65][66]. Early trajectory simulations on the dynamics of Morse chains [58][59][60][61] showed that simple bond stretching or force criteria for bond rupture were inadequate, in that apparently broken bonds were observed to reform (bond healing).…”

Section: Introductionmentioning

confidence: 99%

“…Previous theoretical work has suggested that dissociation of atomic chains under stress is not amenable to simple statistical approaches [40,[58][59][60][61][62][63][64][65][66]. Early trajectory simulations on the dynamics of Morse chains [58][59][60][61] showed that simple bond stretching or force criteria for bond rupture were inadequate, in that apparently broken bonds were observed to reform (bond healing).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Bond breaking in a Morse chain under tension: Fragmentation patterns, higher index saddles, and bond healing

Mauguière

Collins

Ezra

et al. 2013

The Journal of Chemical Physics

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We investigate the fragmentation dynamics of an atomic chain under tensile stress. We have classified the location, stability type (indices), and energy of all equilibria for the general n-particle chain, and have highlighted the importance of saddle points with index >1. We show that for an n = 2-particle chain under tensile stress the index 2 saddle plays a central role in organizing the dynamics. We apply normal form theory to analyze phase space structure and dynamics in a neighborhood of the index 2 saddle. We define a phase dividing surface (DS) that enables us to classify trajectories passing through a neighborhood of the saddle point using the values of the integrals associated with the normal form. We also generalize our definition of the dividing surface and define an extended dividing surface (EDS), which is used to sample and classify all trajectories that pass through a phase space neighborhood of the index 2 saddle at total energies less than that of the saddle. Classical trajectory simulations are used to study fragmentation patterns for the n = 2 chain under tension. That is, we investigate the relative probability for breaking one bond versus concerted fission of several (two, in this case) bonds. Initial conditions for trajectories are obtained by sampling the EDS at constant energy. We sample trajectories at fixed energies both above and below the energy of the saddle. The fate of trajectories (single versus multiple bond breakage) is explored as a function of the location of the initial condition on the EDS, and a connection made to the work of Chesnavich on collision-induced dissociation. A significant finding is that we can readily identify trajectories that exhibit bond healing. Such trajectories pass outside the nominal (index 1) transition state for single bond dissociation, but return to the potential well region, possibly several times, before ultimately dissociating.

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