Chemical Application of Density Functional Theory

密度泛函理论方法是目前理论化学中最常用的计算方法之一，具有好的计算精度和较低的计算花费等优点。密度泛函计算方法目前已广泛应用于化学、物理、材料、生物等学科领域的理论研究。本文应用密度泛函理论，对分子内结构环境对解离能的影响、mDTABN分子内电荷转移、星际分子的结构与稳定性等进行了计算研究，获得的主要结果如下： 一、分子内结构环境对解离能的影响 化学键是最基本的化学概念之一，相关的理论和实验研究一直为人们所重视。键能作为表征化学键的重要参数，被广泛用于研究化合物的化学反应活性及其热力学性质。通过对具有相同化学键而分子内结构环境不同的系列分子进行了计算研究，讨论了化学键结构环境对解离能的影响...The density functional theory (DFT) as one of the most popular methods in the theoretical chemistry currently has been widely used in chemistry, physics, materials science, and biology. In the present study, we applied DFT to explore the effect of intramolecular structural environment on bond dissociation energies, the intramolecular charge transfer of mDTABN, and the structure and stability of C2...学位：理学硕士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：2052007115097

Effect of Intramolecular Structural Environment on Bond Dissociation Energies

The density functional calculations were used to explore the dissociation energies of [N(CH3)4]+ and [P(CH3)4]+ and their derivatives from substitution of H for CH3.The results show that the dissociation energies of C—N and C—P bonds gradually increase as the number of hydrogen atoms bonded to N or P increases in the derivatives,showing a remarkable effect of the intramolecular structural environment on the dissociation of the bonds.This dependence of bond dissociation energies on the local structural environment can be ascribed to the hyperconjugation interactions between the C—H bond and lone single electron of N or P.On the basis of NBO analyses,the bonding properties of dissociated fragments and their effects on dissociation energies were discussed.国家自然科学基金(批准号:20673087,20733002,20873105)资

Effect of Intramolecular Structural Environment on Bond Dissociation Energies

The density functional calculations were used to explore the dissociation energies of [N(CH3)(4)](+) and [P(CH3)(4)](-) and their derivatives from substitution of H for CH3. The results show that the dissociation energies Of C-N and C-P bonds gradually increase as the number of hydrogen atoms bonded to N or P increases in the derivatives, showing a remarkable effect of the intramolecular structural environment on the dissociation of the bonds. This dependence of bond dissociation energies on the local structural environment can be ascribed to hyperconjugation interactions between the C-H bond and lone single electron of N or P. On the basis of NBO analyses, the bonding properties of dissociated fragments and their effects oil dissociation energies were discussed