Reactive force field for electrophilic substitution at an aromatic system in twin polymerization

- Modeling electrophilic substitution of twin polymerization with ReaxFF.
- ReaxFF parametrization from literature fail to reproduce this chemical reaction step.
- Development of appropriate ReaxFF parametrization for this chemical reaction step.
- Comparison with PW6B95-D3 DFT reference calculation for analyzed systems.

Twin polymerization is a new synthesis concept, which enables the formation of two different macromolecular structures from organic-inorganic hybrid materials in one single process step. To gain insights into formation processes we implement a first-principles-based ReaxFF reactive force field for C/H/O/Si for the initial electrophilic substitution of an aromatic system. We show that established parametrizations that have been developed to model chemical reactions of (hydro) carbon or carbon nanotubes systems successfully cannot reproduce this reaction although they include the same chemical elements and in parts same reaction mechanisms. Thus, we develop a new parametrization being capable in reproducing this aromatic reaction properly and compare it to the established ones to identify the differences.