Tim S. Totton

A First Principles Development of a General Anisotropic Potential for Polycyclic Aromatic Hydrocarbons

Standard empirical atom-atom potentials are shown to be unable to describe the binding of polycyclic aromatic hydrocarbon (PAH) molecules in the variety of configurations seen in clusters. The main reason for this inadequacy is the lack of anisotropy in these potentials. We have constructed an anisotropic atom-atom intermolecular potential for the benzene molecule from first principles using a symmetry-adapted perturbation theory based on density functional theory (SAPT(DFT)), interaction energy calculations and the Williams-Stone-Misquitta method for obtaining molecular properties in distributed form. Using this potential as a starting point, we have constructed a transferable anisotropic potential to model intermolecular interactions between PAHs. This new potential has been shown to accurately model interaction energies for a variety of dimer configurations for four different PAH molecules, including certain configurations which are poorly modeled with current isotropic potentials. It is intended that this potential will form the basis for further work on the aggregation of PAHs.

First-Principles Thermochemistry for the Combustion of a TiCl4 and AlCl3 Mixture

AlCl(3) is added in small quantities to TiCl(4) fed to industrial reactors during the combustion synthesis of titanium dioxide nanoparticles in order to promote the rutile crystal phase. Despite the importance of this process, a detailed mechanism including AlCl(3) is still not available. This work presents the thermochemistry of many of the intermediates in the early stages of the mechanism, computed using quantum chemistry. The enthalpies of formation and thermochemical data for AlCl, AlO, AlOCl, AlOCl(2), AlO(2), AlO(2)Cl, AlOCl(3), AlO(2)Cl(2), AlO(3)ClTi, AlO(2)Cl(2)Ti, AlO(2)Cl(4)Ti, AlOCl(5)Ti, AlO(2)Cl(3)Tia (isomer-a), AlO(3)Cl(2)Ti, AlO(2)Cl(5)Ti, AlOCl(4)Ti, AlO(2)Cl(3)Tib (isomer-b), AlCl(7)Ti, AlCl(6)Ti, Al(2)Cl(6), Al(2)O(2)Cl, Al(2)O(2)Cl(3), Al(2)O(3)Cl(2), Al(2)O(2)Cl(2), Al(2)OCl(4), Al(2)O(3), and Al(2)OCl(3) were calculated using density functional theory (DFT). A full comparison between a number of methods is made for one of the important species, AlOCl, to validate the use of DFT and gauge the magnitude of errors involved with this method. Finally, equilibrium calculations are performed to try to identify which intermediates are likely to be most prevalent in the high temperature industrial process and as a first attempt to characterize the nucleation process.

Assessing the polycyclic aromatic hydrocarbon anisotropic potential with application to the exfoliation energy of graphite.

In this work we assess a recently published anisotropic potential for polycyclic aromatic hydrocarbon (PAH) molecules (J. Chem. Theory Comput. 2010, 6, 683-695). Comparison to recent high-level symmetry-adapted perturbation theory based on density functional theory (SAPT(DFT)) results for coronene (C(24)H(12)) demonstrate the transferability of the potential while highlighting some limitations with simple point charge descriptions of the electrostatic interaction. The potential is also shown to reproduce second virial coefficients of benzene (C(6)H(6)) with high accuracy, and this is enhanced by using a distributed multipole model for the electrostatic interaction. The graphene dimer interaction energy and the exfoliation energy of graphite have been estimated by extrapolation of PAH interaction energies. The contribution of nonlocal fluctuations in the π electron density in graphite have also been estimated which increases the exfoliation energy by 3.0 meV atom(-1) to 47.6 meV atom(-1), which compares well to recent theoretical and experimental results.