Creation, migration, and termination of conformational defects in poly(1,4-t r a n s-butadiene) in form II and in the inclusion complex in perhydrotriphenylene

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Abstract
The histories of the conformational defects created by transitions between anticlinal± states, either singly or correlated as next‐nearest neighbors, have been studied using molecular dynamics trajectories computed for a chain of poly(1,4‐trans‐butadiene) in form II and in the inclusion complex with perhydrotriphenylene. The most likely fate of a newly created conformational defect is immediate reversion to the preferred conformation. The remaining defects can undergo diffusion. The average contour lengths for the paths covered in the diffusion are on the order of ten CH–CH2 bonds for a long poly(1,4‐trans‐butadiene) in the inclusion complex in perhydrotriphenylene. The diffusion is terminated either by loss of the defect out the end of the chain, or by the annihilation of two defects that encounter one another. The average time between hops is much shorter for the chain in the inclusion complex than for the chain in form II. The time‐averaged number of defects in methyl terminated decamers is virtually identical in the two systems. For much longer chains, the poly(1,4‐trans‐butadiene) in the inclusion complex should contain more defects than the chain in form II.