The role of molecular properties on the dimerization of aromatic compounds

作     者：Elvati, Paolo Turrentine, Kirk Violi, Angela 

作者机构：Department of Mechanical Engineering University of Michigan Ann ArborMI48109-2125 United States Departments of Chemical Engineering Biomedical Engineering Macromolecular Science and Engineering Biophysics Program University of Michigan Ann ArborMI United States 

出 版 物：《arXiv》 (arXiv)

年 卷 期：2017年

核心收录：

主　　题：Molecular dynamics 

摘      要：Recent results have shown the presence and importance of oxygen chemistry during the growth of aromatic compounds, leading to the formation of oxygenated structures that have been identified in various environments. Since the formation of polycyclic aromatic compounds (PAC) bridge the formation of gas-phase species with particle inception, in this work we report a detailed analysis of the effects of molecular characteristics on physical growth of PAC via dimerization. We have included oxygen content, mass, type of bonds (rigid versus rotatable), and shape as main properties of the molecules and studied their effect on the propensity of these structures to form homo-molecular and hetero-molecular dimers. Using enhanced sampling molecular dynamics techniques, we have computed the free energy of dimerization in the temperature range 500-1680 K. Initial structures used in this study were obtained from experimental data. The results show that although the effects of shape, presence of oxygen, mass, and internal bonds are tightly intertwined, and their relative importance changes with temperature. In general, mass and the presence of rotatable bonds are the best indicators. The results provide knowledge on the inception step and the role that particle characteristics play during inception. In addition, our study highlights the fact that current models that use stabilomers as monomers for physical aggregation are overestimating the importance of this process during particle nucleation. Copyright © 2017, The Authors. All rights reserved.