Dynamical Behavior of Aromatic Trimer Complexes in Unimolecular Dissociation Reaction at High Temperatures. Case Studies on C₆H₆–C₆F₆–C₆H₆ and C₆H₆ Trimer Complexes

Abstract

The intramolecular vibrational energy redistribution (IVR) dynamics during unimolecular dissociation of aromatic trimers at high temperatures is the primary interest of this study. Chemical dynamics simulations are performed for the unimolecular dissociation of benzene–hexafluorobenzene–benzene (Bz-HFB-Bz) and benzene trimer (Bz-trimer) complexes at a temperature range of 1000–2000 K. Partial dissociation of both the complexes is observed, which leads to a dimer and a monomer in the dynamics. However, the probability of such dissociation was found much lower in the case of the Bz-trimer, which further decreases with the increase of temperature. The rate of partial dissociation of Bz-HFB-Bz is faster at 1500, 1800, and 2000 K, whereas the rate of complete dissociation of the Bz-trimer is significantly faster than Bz-HFB-Bz at all temperatures. This is just the opposite of the corresponding dimer’s dissociation, where benzene–hexafluorobenzene (Bz-HFB) dissociates at a faster rate than the benzene dimer (Bz-dimer). Thus, the dissociation dynamics of the trimer is different than that of the dimer. Simulations with excited intramolecular and intermolecular modes of the trimer complexes reveal that energy flows from intermolecular to intramolecular modes of Bz-HFB-Bz more freely than the Bz-trimer, and the dissociation process becomes slower for the former. Calculated activation energies for both types of dynamics are much lower than the corresponding binding energies, which may be due to the anharmonicity. The Arrhenius equation with an anharmonic correction factor is considered to recalculate the activation energy and pre-exponential factor