Detailed structures and mechanism of polymer solvation

In the present study, we simulated a model system, PE in biphenyl, to gain the insight into the detailed solvation structures and the molecular mechanism of polymer chain solvation. Using atomistic molecular dynamics (MD) simulation, it was found that when the biphenyl is far from PE chain or in the bulk, the dihedral angle of the two rings in the solvent molecule are approximately 32 degrees. But, the dihedral angel is about 27 degrees when the biphenyls are very close to the PE chain. In the first solvation shell, the orientation angle of the biphenyl long axis to the chain segment backbone was found to be enhanced around two values: approximately 0 and approximately 60 degrees. The detailed solvation structures found here include all dyad conformations (TT, TG, TG', GT, GG, GG', G'T, G'G, and G'G') and vary as a function of the distance between PE chain and biphenyls in the first solvation shell. The closer the the solvent molecule to the PE segment, the higher the TT conformation fraction response is. The other dyad conformations such as TG, GG', etc. undergo different decreases, respectively. This study shows that the solvation even in the Theta condition makes the overall size expansion or the chain stretched. Such a cooperative change was examined here and found not due to generating or losing a conformational state but due to a change in conformational distribution. This change occurs in the middle location of the chain instead of the chain end locations.