A theoretical study of the structure and vibrations of 2,4,6-trinitrotolune

被引:114
作者
Clarkson, J
Smith, WE
Batchelder, DN
Smith, DA
Coats, AM
机构
[1] Univ Strathclyde, Dept Pure & Appl Chem, Glasgow G1 1XL, Lanark, Scotland
[2] Univ Leeds, Dept Phys & Astron, Leeds LS2 9JT, W Yorkshire, England
[3] Univ Aberdeen, Dept Chem, Aberdeen AB24 3UE, Scotland
关键词
trinitrotoluene; density functional theory; vibrational analysis;
D O I
10.1016/S0022-2860(03)00024-3
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Theoretical calculations of the structure, internal rotations and vibrations of 2,4,6-trinitrotolune, TNT, in the gas phase were performed at the B3LYP/6-31G* and B3LYP/6-311 + G** levels of theory. Two genuine energy minimum structures were found. In both structures the 4-nitro, group is planar to the phenyl ring, while the 2,6-nitro groups are slightly out of plane with the phenyl ring due to steric interaction with the methyl group. The two structures are related by internal rotations of the methyl and 2, or 6-nitro group. The lowest energy route for interconversion. between them is a concerted motion of the methyl group and 2 or 6 nitro group in a 'cog wheel' type of mechanism. The geometry of the low energy structure A is closest to that observed in the crystal structures of TNT, where all three nitro groups are out of plane with the phenyl ring. FTIR and Raman spectra of solid TNT and C-13, N-15 enriched TNT are presented and assigned with the help of the B3LYP/6-311 + G** calculations on A. The lower level B3LYP/6-31G* calculation fails to predict the correct vibrational coupling between the nitro and phenyl groups. The B3LYP/6-311 + G** calculation gives a good prediction of the nitro vibrations and the isotopic shifts observed for TNT isotopomers. (C) 2003 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:203 / 214
页数:12
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