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.

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