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Ab initio Study of Electronic Structure and Properties in Crystalline 1,1,3,3,5,5‐Hexaazidocyclotriphosphazene
Author(s) -
HUANG HuiSheng,
ZHANG JianGuo,
ZHANG TongLai,
YANG Li,
ZHENG HuiHui
Publication year - 2008
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.200890158
Subject(s) - chemistry , ab initio , phosphazene , molecule , intermolecular force , crystal structure , crystallography , charge density , molecular orbital , molecular physics , electronic structure , atomic orbital , crystal (programming language) , computational chemistry , electron , physics , organic chemistry , quantum mechanics , polymer , computer science , programming language
The banding and electronic structures of crystalline 1,1,3,3,5,5‐hexaazidocyclotriphosphazene (P 3 N 21 ) have been investigated at DFT‐B3LYP/6‐31G(d) level. Relaxed crystal structure compares well with experimental data. The energy gap is 5.57 eV, indicating that P 3 N 21 is an insulator. The frontier orbital is mainly formed by atomic orbitals of azido group, so it is the most reactive part of the molecule. The intermolecular interaction is strong along the direction that is nearly perpendicular to the phosphazene ring. The distribution of electrostatic potential is quite uneven, so P 3 N 21 has a very high impact sensitivity. The point charge electrostatic potential is very high between the azido groups of the neighboring molecules, which indicates that the crystal lattice in this position may easily be broken and becomes the explosion center when P 3 N 21 is impacted. The overlap populations of P–N α bonds are much less than those of other bonds, therefore the P–N α bonds first rupture by external stimuli, which agrees well with the experimental study of mass spectrum.