Local chain dynamics of a model polycarbonate near glass transition temperature: A molecular dynamics simulation

Constant pressure constant temperature molecular dynamics method is employed to investigate the atomistic scale dynamics of a model Bisphenol A polycarbonate in the vicinity of its glass transition temperature. First, the glass transition temperature and the thermal expansion coefficients of the polymer are predicted by performing simulations at different temperatures. To explore the significance of different modes of motion, various types of time correlation functions are utilized in analyzing the trajectories. In these nanosecond scale simulations, the motion of the chain segments is found to be highly localized with little reorientation of the vectors representing these segments. Detailed analysis of trajectories and the correlation functions of the backbone dihedrals and side methyl groups indicates that they exhibit numerous conformational transitions. The activation energies of the conformational transitions obtained from the simulation are generally larger than the potential barriers for the rotations of these dihedrals, however, both show the same trend. We also have estimated the phenylene ring flip activation energy as 12.6 kcal/mol and the flip frequency as 0.77 MHz at 300 K. These values either fall within the range determined by various NMR spectroscopy experiments or slightly out of the range. The study shows that the conformational transitions between the adjacent dihedrals are strongly correlated. Three basic cooperative modes are identified from the simulation. They are: a positive synchronous rotation of two phenylene rings, a negative synchronous rotation of two phenylene rings, and a carbonate group rotation. Above the glass transition temperature, the large scale cooperative motions become much more significant.