Pyrolysis of the homoleptic azido complex [P(N3)6]− was simulated using density functional theory based molecular dynamics and analyzed further using electronic-structure calculations in atom-centered basis sets to calculate the geometries and electronic structures. Simulations at 600 and 1200 K predict a thermally induced and, on the simulation time scale, irreversible dissociation of an azido anion. The ligand loss is accompanied by a barrierless (free-energy) transition of the geometry of the complex coordination sphere from octahedral to trigonal bipyramidal. [P(N3)5] is fluxional and engages in pseudorotation via a Berry mechanism.
- SPACE GAUSSIAN PSEUDOPOTENTIALS, THERMAL-DECOMPOSITION, METHYL AZIDE, GAS-PHASE, AB-INITIO, STRUCTURAL-CHARACTERIZATION, MOLECULAR-DYNAMICS, CRYSTAL-STRUCTURE, ETHYL AZIDE, THIN-FILMS