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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

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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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Radical Chain-Growth Polymerization: Overview01:10

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Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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Step-Growth Polymerization: Overview01:03

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
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Radical Chain-Growth Polymerization: Mechanism01:09

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The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this species into...
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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Molecular Weight of Step-Growth Polymers01:08

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Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
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Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
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Accelerating ring-polymer molecular dynamics with parallel-replica dynamics.

Chun-Yaung Lu1, Danny Perez2, Arthur F Voter2

  • 1Department of Energy Resources Engineering, Stanford University, Stanford, CA 94305, USA.

The Journal of Chemical Physics
|July 3, 2016
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Summary
This summary is machine-generated.

Nuclear quantum effects significantly impact light elements at low temperatures. Combining ring-polymer molecular dynamics with parallel replica dynamics enables accurate, long-time simulations of these quantum systems.

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Area of Science:

  • Computational Chemistry
  • Quantum Dynamics
  • Materials Science

Background:

  • Nuclear quantum effects are crucial for light elements, especially at low temperatures.
  • Simulating these effects is challenging due to sluggish dynamics and the need for long time scales.

Purpose of the Study:

  • To develop and validate a novel computational method for simulating quantum dynamics in complex systems.
  • To accurately capture zero-point energy and tunneling effects in infrequent-event processes.

Main Methods:

  • Integration of ring-polymer molecular dynamics (RP) with parallel replica (ParRep) dynamics.
  • Application of the combined RP-ParRep method to benchmark systems.

Main Results:

  • The RP-ParRep method accurately simulates quantum dynamics, including tunneling.
  • Demonstrated capability to reach long time scales in complex systems.
  • Successful application to symmetric Eckart barrier crossing and interstitial helium diffusion in Fe and Fe-Cr alloys.

Conclusions:

  • The RP-ParRep method is a powerful tool for studying quantum dynamics in systems where nuclear quantum effects are important.
  • This approach significantly enhances the ability to simulate infrequent-event systems over extended time scales.