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At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately 105 times per second. These two chair conformers are in equilibrium. The rapid ring flipping results in the interconversion of the axial proton to an equatorial proton and an equatorial to the axial proton. Such interconversions are too rapid and cannot be detected on the NMR timescale. Hence, the NMR spectrometer cannot distinguish between the...
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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
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Energy localization and shape transformations in semiflexible polymer rings.

Yu B Gaididei1, J F R Archilla2, V J Sánchez-Morcillo3

  • 1Bogolyubov Institute for Theoretical Physics, Metrologichna Street 14 B, 03143 Kiev, Ukraine.

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Driven molecular chains transition from circular to polygonal shapes when energy input exceeds a critical threshold. This nonequilibrium phase transition leads to localized energy distribution and altered chain dynamics.

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Area of Science:

  • Physics, Condensed Matter
  • Materials Science
  • Chemical Physics

Background:

  • Molecular chains exhibit complex dynamics influenced by external fields and internal couplings.
  • Understanding shape transformations in driven systems is crucial for designing novel materials and devices.

Purpose of the Study:

  • To investigate shape transformations in driven and damped molecular chains.
  • To analyze the effect of external fields on the chain's bending rigidity and overall shape.
  • To explore the phenomenon of nonequilibrium phase transitions in molecular aggregates.

Main Methods:

  • Theoretical modeling of weakly coupled molecular subunits in a closed chain.
  • Analysis of the interplay between internal excitations and bending degrees of freedom.
  • Study of the system's response to spatially homogeneous, time-periodic external fields.

Main Results:

  • In the absence of driving, the molecular chain adopts a circular shape.
  • Exceeding a critical energy input triggers a nonequilibrium phase transition, deforming the chain into elliptical or polygonal shapes.
  • Excitation energy becomes nonuniformly distributed, localizing in flatter regions of the chain.

Conclusions:

  • External driving and damping can induce significant shape transformations in molecular chains.
  • Nonequilibrium phase transitions are observable in these systems, leading to complex emergent behaviors.
  • The findings have implications for understanding energy localization and dynamics in soft matter systems.