Internal rotation of amino and nitro groups in TATB: MP2 versus DFT (B3LYP)

被引：31

作者：

Manaa, MR ^{[1
]}

Gee, RH ^{[1
]}

Fried, LE ^{[1
]}

机构：

[1] Lawrence Livermore Natl Lab, Chem & Mat Sci Directorate, Livermore, CA 94551 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2002年 / 106卷 / 37期

关键词：

D O I：

10.1021/jp0259972

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：

We report second-order Moller-Plesset (MP2) and density functional (B3LYP) fully optimized amino and nitro group torsional potential barriers in 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), a molecule with unusually strong intramolecular hydrogen bonding. The calculated barriers show optimum values of 17.0 (25.5) kcal/mol for the amino group and 5.6 (10.5) kcal/mol for the nitro group rotation at the MP2 (B3LYP) level. The large barrier associated with the amino rotation is due to the double-bond character of the respective C-N bond. Because the B3LYP results are 50-87% higher in energy than those provided by MP2, a more detailed comparison with other functionals and higher-level ab initio methods is needed for an accurate description of these intramolecular motions.

引用

页码：8806 / 8810

页数：5

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