Describing free-radical polymerization reactions with a stochastic approach | Poster Board #805

Reliable thermodynamic and kinetic properties of free-radical polymerization are essential for the synthesis of both primary polymeric materials and specialty materials. Acquiring this insightful data presents difficulty due to deficiencies of mean field theory and substantial computational expenses of composite methods. A stochastic approach presents a potential solution to these matters. Instead of solving the ground state energy with conventional integration grids, Fixed-Node Diffusion Monte Carlo (FN-DMC) samples the electrons' positions in real space and then imposes an exponential projection of the time dependent Schrödinger equation to obtain the true ground state wavefunction. In this poster session, a detailed analysis on principle parameters affiliated with FN-DMC is presented to establish a basis for larger polymers. FN-DMC is then applied to free-radical addition reactions related to reversible addition-fragment chain transfer (RAFT) polymerization, where activation energies and reaction enthalpies are compared to experiment and current benchmarking methods.