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Cooperative Effects and Strengths of Hydrogen Bonds in Open-Chain cis-Triaziridine Clusters (n = 2−8):  A DFT Investigation

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journal contribution
posted on 16.02.2006 by Hua-Jie Song, He-Ming Xiao, Hai-Shan Dong, Wei-Hua Zhu
We employ DFT/B3LYP method to investigate linear open-chain clusters (n = 2−8) of the cis-triaziridine molecule that is a candidate molecule for high energy density materials (HEDM). Our calculations indicate that the pervasive phenomena of cooperative effects are observed in the clusters of n = 3−8, which are reflected in changes in lengths of N···H hydrogen bonds, stretching frequencies, and intensities of N−H bonds, dipole moments, and charge transfers as cluster size increases. The n(N) → σ*(N−H) interactions, i.e., the charge transfers from lone pairs (n(N)) of the N atoms into antibonds (σ*) of the N−H bonds acting as H-donors, can be used to explain the observed cooperative phenomena. The approaches based upon natural bond orbital (NBO) method and theory of atoms in molecule (AIM) to evaluating N···H strengths are found to be equivalent. In the process of N···H bonding, cooperative nature of n(N) → σ*(N−H) interactions promotes formation of stronger N···H bonds as reflected in increases in the capacities of cis-triaziridine clusters to concentrate electrons at the bond critical points of N···H bonds. The calculated nonadditive energies also show that the cooperative effects due to n(N) → σ*(N−H) interactions indeed provide additional stabilities for the clusters.