Electronically nonadiabatic decomposition mechanisms of clusters of zinc and dimethylnitramine

- Decomposition mechanisms of dimethylnitramine-zinc clusters are explored.
- Decomposition pathways are electronically nonadiabatic.
- ONIOM-CASSCF methodology is employed.
- Zn cluster facilitates exothermic nitro-nitrite isomerization pathway.
- NO is predicted to be the initial decomposition product.

Electronically nonadiabatic decomposition mechanisms of dimethylnitramine (DMNA) in presence of zinc metal clusters are explored. Complete active space self-consistent field (CASSCF) calculation is employed for DMNA-Zn and ONIOM (Our own N-layered integrated molecular orbital and molecular mechanics) methodology is coupled with CASSCF methodology for DMNA-Zn10 cluster. Present computational results show that DMNA-Zn clusters undergo electronically nonadiabatic reactions, rendering nitro-nitrite isomerization followed by NO elimination. The overall reactions are also found to be highly exothermic in nature. This is the first report on electronically nonadiabatic decomposition pathways of DMNA-Znn neutral clusters.