Computational simulations of hydrolysis of phosphazene oligomer utilizing atom‐centered density matrix propagation

Density functional theory (DFT) calculations, including the ab initio molecular dynamics method, atom‐centered density matrix propagation (ADMP), were used to investigate the hydrolysis reaction of a dichlorophosphazene trimer. The model trimer, intermediate structures and the product of the first step of hydrolysis, were optimized using DFT with the B3LYP density functional, followed by a 600 fs ADMP simulation. Natural bond order analysis (NBO) was used to determine atomic charges and occupancy of the bond orbitals and the lone pair orbitals of the molecule at various points along the simulation pathway. The simulation successfully shows dissociation of the trimer backbone into two distinct product molecules, shown through both increasing separation of the product units and through the more thorough NBO analysis of the bond orbitals. © 2012 Wiley Periodicals, Inc.