An ab initio study of intermolecular interactions of nitromethane dimer and nitromethane trimer

被引:20
作者
Li, JS [1 ]
Zhao, F [1 ]
Jing, FQ [1 ]
机构
[1] SW Inst Fluid Phys, Lab Shock Wave & Detonat Phys Res, Mianyang 621900, Sichuan, Peoples R China
关键词
nitromethane dimer; nitromethane trimer; intermolecular interaction; density functional theory B3LYP method; MP2; method;
D O I
10.1002/jcc.10179
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Different geometries of nitromethane dimer and nitromethane trimer have been fully optimized employing the density functional theory B3LYP method and the 6-31++G** basis set. Three-body interaction energy has been obtained with the ab initio supermolecular approach at the levels of MP2/6-31++G**//B3LYP/6-31++G** and MP2/aug-cc-pVDZ//B3LYP/6-31++G**. The internal rotation of methyl group induced by intermolecular interaction has been observed theoretically. For the optimized structures of nitromethane dimer, the strength of C-H...O-N H-bond ranges from -9.0 to -12.4 kJ mol(-1) at the MP2/aug-cc-pVDZ//B3LYP/6-31++G** level, and the B3LYP method underestimates the interaction strength compared with the MP2 method, while MP2/6-31++G**//B3LYP/631++G** calculated DeltaE(C) is within 2.5 kJ mol(-1) of the corresponding value at the MP4(SDTQ)/6-31G**//B3LYP/6-31++G** level. The analytic atom-atom intermolecular potential has been successfully regressed by using the MP2/6-31++G**//B3LYP/6-31++G** calculated interaction energies of nitromethane dimer. For the optimized structures of nitromethane trimer the three-body interaction energies occupy small percentage of corresponding total binding energies, but become important for the compressed nitromethane explosive. In addition, it has been discovered that the three-body interaction energy in the cyclic nitromethane trimer is more and more negative as intermolecular distances decrease from 2.2 to 1.7 Angstrom.
引用
收藏
页码:345 / 352
页数:8
相关论文
共 28 条
[1]   Non-conventional hydrogen bonds [J].
Alkorta, I ;
Rozas, I ;
Elguero, J .
CHEMICAL SOCIETY REVIEWS, 1998, 27 (02) :163-170
[2]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[3]   CALCULATION OF SMALL MOLECULAR INTERACTIONS BY DIFFERENCES OF SEPARATE TOTAL ENERGIES - SOME PROCEDURES WITH REDUCED ERRORS [J].
BOYS, SF ;
BERNARDI, F .
MOLECULAR PHYSICS, 1970, 19 (04) :553-&
[4]   ON THE CONNECTION BETWEEN THE SUPERMOLECULAR MOLLER-PLESSET TREATMENT OF THE INTERACTION ENERGY AND THE PERTURBATION-THEORY OF INTERMOLECULAR FORCES [J].
CHALASINSKI, G ;
SZCZESNIAK, MM .
MOLECULAR PHYSICS, 1988, 63 (02) :205-224
[5]   ANALYSIS OF THE POTENTIAL-ENERGY SURFACE OF AR-NH3 [J].
CHALASINSKI, G ;
CYBULSKI, SM ;
SZCZESNIAK, MM ;
SCHEINER, S .
JOURNAL OF CHEMICAL PHYSICS, 1989, 91 (12) :7809-7817
[6]   THERMODYNAMIC PROPERTIES OF GAS-PHASE HYDROGEN-BONDED COMPLEXES [J].
CURTISS, LA ;
BLANDER, M .
CHEMICAL REVIEWS, 1988, 88 (06) :827-841
[7]  
Frisch M.J., 2016, Gaussian 16 Revision C. 01. 2016, V16, P01
[8]   Structure, energetics, and dynamics of the nucleic acid base pairs:: Nonempirical ab initio calculations [J].
Hobza, P ;
Sponer, J .
CHEMICAL REVIEWS, 1999, 99 (11) :3247-3276
[9]   INTERMOLECULAR INTERACTIONS BETWEEN MEDIUM-SIZED SYSTEMS - NONEMPIRICAL AND EMPIRICAL CALCULATIONS OF INTERACTION ENERGIES - SUCCESSES AND FAILURES [J].
HOBZA, P ;
ZAHRADNIK, R .
CHEMICAL REVIEWS, 1988, 88 (06) :871-897
[10]  
Jeffrey G. A., 1997, INTRO HYDROGEN BONDI