Simulation of Reaction Dynamics: Nonadiabatic and Solvation Effects

摘要

This research involved four projects centered on the design of theoretical and computational approaches to predict promising energetic materials and to guide the efficient synthesis of these materials. First, mixed quantum/classical methodology was developed for the simulation of photochemical reactions, which could play an important role in the design and synthesis of energetic materials. Second, the time-dependent self-consistent-field reaction path Hamiltonian method was developed for the calculation of the real-time quantum dynamics of polyatomic reactions. Third, a new approach for investigating the solvent effects of fundamental organic reactions was developed in order to aid in the efficient synthesis of energetic materials. This approach combined electronic structure calculations with reactive flux molecular dynamics calculations based on a reaction path Hamiltonian. Application of this approach to two fundamental organic reactions provided insight into the dynamical role of solvent and elucidated possible reaction mechanisms. Fourth, the Fourier grid Hamiltonian multi configurational self-consistent-field and partial multidimensional grid generation methods were developed for the efficient calculation of multidimensional hydrogen vibrational wavefunctions. These two methods enable the simulation of hydrogen transfer reactions required for the synthesis of polyhedral oligomeric silsesquioxanes, which are used in coatings that are resistant to extreme conditions such as heat and abrasion.