Host/guest simulation of fluorescent probes adsorbed into low-density polyethylene, 1 - Excimer formation of 1,3-Di(1-pyrenyl)propane

Abstract

Molecular dynamics and Rotational Isomer State/Monte Carlo techniques with a Dreiding 1.01 Force Field are employed to study the excimer formation of isolated 1,3-di(1-pyrenyl)propane and the probe adsorbed into a low-density polyethylene (LDPE) matrix model. The probability of formation of each molecular conformer at several temperatures was calculated using these theoretical techniques. Conformational statistical analysis of the four torsion angles (phi (1), phi (2), theta (1), theta (2)) of Py3MPy showed that the angles -C-C-ar- (phi (1), phi (2)) present two states c(+/-) = +/- 90 degrees; and the angles -C-C- (theta (1), theta (2)), the three trans states = 180 degrees, g(+/-) = +/- 60 degrees. The correlation of theta (1)-theta (2) torsion angles showed that the most probable pairs were g(+)g(-) and g(-)g(+) for the excimer-like specimens, although these angles are distorted because of interactions with the polymer matrix. The temperature dependence of the excimer-formation probability revealed that this process was thermodynamically controlled in the isolated case. When the probe was adsorbed into the LDPE matrix, the excimer formation process was reversed at T = 375 K. At T > 375 K, the behavior was similar to the isolated case but, at T < 375 K, excimer formation probability increased with temperature as found experimentally by steady-state fluorescence spectroscopy. This temperature was coincident with the onset of the LDPE melting process, determined experimentally by thermal analysis. [GRAPHICS] Initial structures of Py3MPy (top) and of LDPE (bottom).