[CH3ONO2]H+正离子与R-OH型分子相互作用的DFT研究

用密度泛函(DFT)(B_³LYP) 方法,在6-31G(d,p)基组水平上优化了两种质子化的硝酸甲酯异构体几何构型和能量,研究了异构体与H₂O、CH₃OH等分子之间的氢键的相互作用,提出了氢键超分子复合物的两种平面结构。研究发现在酯位质子化异构体的相对稳定性高于在硝氧位质子化的异构体。但当异构体在液相中与ROH类分子发生分子间相互作用后这一顺序发生了反转,说明了该体系中的分子间相互作用对异构体较强的影响。

Theoretical study of molecular interaction between [CH3ONO2]H+ and R-OH

In this paper two kinds of structures of hydrogen bonded complex (HBC), formed by molecular interaction between CH 3ONO 2]H + and several small molecules like H 2O and CH 3OH, were studied. The energies and geometry of the HBCs were optimized using DFT method at the level of B3LYP/6-31G(d,p). In the energetic point of view, the results indicate that the methyl nitrate protonated at the ester oxygen is more stable than that protonated at the nitro group oxygen, and the order about the stability of corresponding HBCs become opposite, when the molecular interaction being considered. So the hydrogen bonding interaction is important when studying stability and activity of methyl nitrate protonated, especially in the liquid phase reaction