caa a22 4500 605513767 CHVBK 20210128100701.0 cr unu---uuuuu 210128e20151101xx s 000 0 eng 10.1007/s00894-015-2842-7 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2842-7 A theoretical investigation into the strength of N-NO2 bonds, ring strain and electrostatic potential upon formation of intermolecular H-bonds between HF and the nitro group in nitrogen heterocyclic rings C n H2 n N-NO2 ( n  = 2-5), RDX and HMX [Elektronische Daten] [Bao-guo Wang, Fu-de Ren, Wen-jing Shi] Changes in N-NO2 bond strength, ring strain energy and electrostatic potential upon formation of intermolecular H-bonds between HF and the nitro group in nitrogen heterocyclic rings C n H2n N-NO2 (n = 2-5), RDX and HMX were investigated using DFT-B3LYP and MP2(full) methods with the 6-311++G(2df,2p) and aug-cc-pVTZ basis sets. Analysis of electron density shifts was also carried out. The results indicate that H-bonding energy correlates well with the increment of ring strain energy. Upon complex formation, the strength of the N-NO2 trigger-bond is enhanced, suggesting reduced sensitivity, while judged by the increased ring strain energy, sensitivity is increased. However, some features of the molecular surface electrostatic potential, such as a local maximum above the N−NO2 bond and ring, σ + 2 and electrostatic balance parameter ν, remain essentially unchanged upon complex formation, and only a small change in the impact sensitivity h 50 is suggested. It is not sufficient to determine sensitivity solely on the basis of trigger bond or ring strain; as a global feature of a molecule, the molecular surface electrostatic potential is available to help judge the change of sensitivity in H-bonded complexes. Graphical Abstract The strengthened N-NO2 bond suggests reduced sensitivity, while it is reverse by theincreased ring strain energy upon the complex formation. However, the molecular surfaceelectrostatic potential (V S) shows the little change of h 50. The V S should be taken into accountin the analysis of explosive sensitivity in the H-bonded complex. Springer-Verlag Berlin Heidelberg, 2015 Intermolecular H-bond nationallicence Ring strain nationallicence Bond dissociation energy nationallicence Sensitivity nationallicence Electrostatic potential nationallicence MP2(full) nationallicence Wang Bao-guo College of Chemical Engineering and Environment, North University of China, 030051, Taiyuan, China aut Ren Fu-de College of Chemical Engineering and Environment, North University of China, 030051, Taiyuan, China aut Shi Wen-jing The Third Hospital of Shanxi Medical University, 030053, Taiyuan, China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/11(2015-11-01), 1-11 1610-2940 21:11<1 2015 21 894 https://doi.org/10.1007/s00894-015-2842-7 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2842-7 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Wang Bao-guo College of Chemical Engineering and Environment, North University of China, 030051, Taiyuan, China aut NATIONALLICENCE 700 1- Ren Fu-de College of Chemical Engineering and Environment, North University of China, 030051, Taiyuan, China aut NATIONALLICENCE 700 1- Shi Wen-jing The Third Hospital of Shanxi Medical University, 030053, Taiyuan, China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/11(2015-11-01), 1-11 1610-2940 21:11<1 2015 21 894