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Theoretical study of the decomposition mechanism of a series of group III triazides X(N 3 ) 3 (X = B, Al, Ga)
Author(s) -
Ping Cheng Li,
Li Wang Jing,
Xin Sun Ying
Publication year - 2015
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24793
Subject(s) - density functional theory , crystallography , decomposition , singlet state , chemistry , dissociation (chemistry) , group (periodic table) , series (stratigraphy) , planar , stereochemistry , computational chemistry , physics , atomic physics , computer graphics (images) , organic chemistry , computer science , excited state , paleontology , biology
Density functional theory method is used to examine a series of group III triazides X(N 3 ) 3 (X = B, Al, Ga). These compounds, except for the C 3 h planar B(N 3 ) 3 and Al(N 3 ) 3 , are first reported here. C 3 h planar structures are the most energetically favored for all singlet X(N 3 ) 3 systems. Potential‐energy surfaces for unimolecular decompositions of the C 3 h and C S planar X(N 3 ) 3 species have been investigated. Results show that decomposition of B(N 3 ) 3 obeys sequential fashion and follows a four‐step mechanism: (1) B(N 3 ) 3 → NB(N 3 ) 2 + N 2 ; (2) NB(N 3 ) 2 → cyc‐N 2 BN 3 + N 2 ; (3) cyc‐N 2 BN 3 → trigonal‐BN 3 + N 2 ; (4) trigonal‐BN 3 → linear‐NBNN. Decomposition of Al(N 3 ) 3 follows a two‐step mechanism: (1) Al(N 3 ) 3 → NAl(N 3 ) 2 + N 2 ; (2) NAl(N 3 ) 2 → linear‐AlN 3 + 2N 2 . The dissociation of Ga(N 3 ) 3 follows only one‐step mechanism: Ga(N 3 ) 3 → angular‐GaN 3 + 3N 2 . These findings may be helpful in understanding the decomposition mechanisms of group III triazides as well as the possible mechanism for XN film generation. © 2014 Wiley Periodicals, Inc.