caa a22 4500 60551092X CHVBK 20210128100648.0 cr unu---uuuuu 210128e20150601xx s 000 0 eng 10.1007/s00894-015-2699-9 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2699-9 A theoretical prediction of the possible trigger linkage of CH3NO2 and NH2NO2 in an external electric field [Elektronische Daten] [Fu-de Ren, Duan-lin Cao, Wen-jing Shi, Min You, Man Li] The effects of an external electric field on the C/N-NO2 bond with C/N-H and N-O bonds in CH3NO2 or NH2NO2 were compared using the DFT-B3LYP and MP2 methods with the 6-311++G(2d,p) and aug-cc-pVTZ basis sets. The results show that such fields have a minor effect on the C-N or C-H bond but a major effect on the N-O bond in CH3NO2, while in NH2NO2 electric fields affect the N-N bond greatly but the N-O or N-H bond only slightly. Thus, in CH3NO2, oxygen transfer or unimolecular isomerization to methyl nitrite might precede breaking of the C-N bond in the initial stages of decomposition, and the N-O bond could be the trigger bond in electric fields. In NH2NO2, however, N-N bond rupture may be preferential in an electric field and, consequently, the N-N bond might always be the real trigger bond. Atoms in molecules and natural bond orbital delocalization analyses, together with examination of shifts in electron density and frequencies support the above viewpoints. Forty-eight good linear correlations were found along the different field orientations at different levels of theory, including those between field strength (E) and changes in N−O/N−N bond length (ΔR N−O/N−N), ρ (N−O/N−N) values [Δρ (N−O/N−N), or stretching frequencies of the N−O/N−N bond (ΔυN−O/N−N). Graphical Abstract External electric fields have a major effect on the N-O or N-N bond inCH3NO2 or NH2NO2 , leading to a possible N-O trigger bond inCH3NO2 or a real N-N trigger bond in NH2NO2 in an electric field Springer-Verlag Berlin Heidelberg, 2015 Trigger linkage nationallicence External electric field nationallicence AIM nationallicence Shifts of electron density nationallicence MP2 nationallicence Ren Fu-de College of Chemical Engineering and Environment, North University of China, 030051, Taiyuan, China aut Cao Duan-lin 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 You Min College of Chemical Engineering and Environment, North University of China, 030051, Taiyuan, China aut Li Man College of Chemical Engineering and Environment, North University of China, 030051, Taiyuan, China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/6(2015-06-01), 1-9 1610-2940 21:6<1 2015 21 894 https://doi.org/10.1007/s00894-015-2699-9 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/s00894-015-2699-9 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Ren Fu-de College of Chemical Engineering and Environment, North University of China, 030051, Taiyuan, China aut NATIONALLICENCE 700 1- Cao Duan-lin 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 700 1- You Min College of Chemical Engineering and Environment, North University of China, 030051, Taiyuan, China aut NATIONALLICENCE 700 1- Li Man College of Chemical Engineering and Environment, North University of China, 030051, Taiyuan, China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/6(2015-06-01), 1-9 1610-2940 21:6<1 2015 21 894