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A Covalent‐Like Feature of Intermolecular Hydrogen Bonding in Energetic Molecules 3,6‐Dihydrazino‐s‐tetrazine (DHT)
Author(s) -
Wang Rui,
Wang Jia,
Zhu Yu,
Yu Famin,
Yang Yanqiang,
Wang Zhigang
Publication year - 2021
Publication title -
advanced theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.068
H-Index - 17
ISSN - 2513-0390
DOI - 10.1002/adts.202100179
Subject(s) - intermolecular force , covalent bond , hydrogen bond , molecule , atoms in molecules , chemical physics , dimer , chemistry , tetrazine , delocalized electron , electron localization function , non covalent interactions , computational chemistry , three center two electron bond , molecular orbital , crystallography , electron , valence bond theory , organic chemistry , physics , quantum mechanics
To explore how intermolecular hydrogen bond (H‐bond) interactions enhance the density and stability of energetic molecular systems, the intermolecular H‐bonding nature of different dimer isomers derived from a new‐generation ecofriendly energetic molecule, 3,6‐dihydrazino‐s‐tetrazine is studied. First‐principles calculations showed that the critical point of the electron localization function on H‐bonds (H…N) lines increased with the enhancement of the H‐bond strength, confirming that covalent properties of H‐bonds are more important as their strength is stronger. Further energy decomposition analysis indicates that the induced effect accounts for more than 18% of intermolecular interaction attraction terms in planar isomers, reflecting the indispensable covalent‐like feature of H‐bonds in energetic molecular systems. Moreover, molecular orbitals exhibit clear delocalization characteristics penetrating H‐bond regions, which also provide important evidence for covalent‐like features of H‐bonds. These findings provide new insights to further understand and even regulate the insensitivity of energetic materials.