环五甲撑五硝胺(CRX)结构和性质的DFT预示

The DFT Predictions of the Structure and Property of Cyclopentamethylenepentanitramine*

用密度泛函理论 (DFT)B3LYP方法 ,在 6 31G 基组水平下 ,全优化计算了环五甲撑五硝胺 (CRX)的分子几何和优化构型下的电子结构 .环C -N键长为 0 .144～ 0 .148nm ,N -NO2 键长为 0 .139～ 0 .142nm ;CRX的最高占有MO(HOMO)能级和最低未占MO(LUMO)能级之间的差值ΔEg(5 .2 0 5 4eV)较大 ,预示CRX较稳定 .基于简谐振动分析求得IR谱频率和强度 .运用统计热力学方法 ,求得在 2 0 0～ 12 0 0K的热力学性质C0p ,m、S0 m 和H0 m.还运用Kamlet公式预示了它的爆速和爆压分别为 916 9m/s和 37.88GPa .

The compounds hexahydro-1, 3, 5-trinitro-1, 3, 5-triazine ( RDX) and octohydro-1, 3, 5, 7-tetranitro-1, 3,5, 7-tetrazocine ( HMX) are two well known energetic materials. The Cyclopentamethylenepentanitramine is called CRX. The full geometry optimization and normal-mode analysis of CRX are performed using nonlocal density functional theory ( DFT) method. The density functional used in this study is B3LYP and the basis set empolyed is 6-31G(*). Normal-mode analyses are used to characterize the stable point and to determine the harmonic vibrational frequencies. The standard thermodynamic properties (C-P,m(0), S-m(0) and H-m(0)) within 200 similar to 1200 K are calculated using the statistical thermodynamic method. The conformation of CRX is about C-2 symmetry. The dipole moment is 6.137 Dabye. C-N bond lengths and N-NO2 bond lengths are among 0.144 similar to 1. 48nm, 0.139 similar to 0.142 nm, respectively. The difference between the energy of the highest occupied molecular orbital ( HOMO) and that of the lowest unoccupied molecular orbital ( LUMO) is 5.2054 eV, which predicts that CRX is more stable. All the thermodynamic quantities increase as the temperature goes up. This is because when the temperature is lower the main contributions to the thermodynamic functions are from the translations and rotations of molecules. But at the higher temperatures, the vibrations contribute more to their thermodynamic functions, which results in the increase of the thermodynamic functions. In addition, the added extent for both C,m and S, decreases with the increasing temperature, but increases for H-m(o). Defined as the volume inside a contour of 0.001 electrons/bohr(3) density, the molar volume of CRX is computed, using the Monte-Carlo method based on the spatial structure obtained from full optimization at B3LYP/6-31G(*) level. The obtained molar volume is 200. 499 cm(3)/mol. Then the calculated density is 1. 846 g/cm(3). It is greater than that of both RDX and HMX. The detonation velocity and pressure of the titled compound are predicted to be 9169 m/s and 37.88 GPa respectively by Kamlet formula. They are higher than those of RDX and HMX.