【作者】 王宝俊；

【导师】 谢克昌；

【作者基本信息】 太原理工大学 ， 化学工程与技术， 2006， 博士

【摘要】 量子化学计算方法在煤化学中的应用，已逐步深入到探索煤的结构与反应性之间的关系，逐渐形成了一个新的研究方向。目前量子化学计算方法已经为处理煤结构提供了一种切实可行的研究手段，这种方法的关键在于选择和构建合理的煤结构模型。因此，针对煤的特定属性构建“煤的局部微观结构模型”，可以为煤的结构与反应性研究提供可靠的理论基础。 本文根据上述思路，构建了7个可以采用量子化学计算方法处理的煤局部微观结构模型：描述煤热化学性质的片断结构模型，描述煤UV-Vis吸收特性的稠环芳香化合物结构模型，描述煤表面电位性质的取代稠环芳烃边缘模型，描述煤的气体吸附的片断结构模型，描述煤中氢键的酚羟基自组合苯酚氢键模型，描述溶剂分子抽提作用的固定结构模型和优化结构模型。针对这些模型用量子化学计算的方法阐述了结构与相关性质的关系。在计算过程中，提出了“多点计算，整体平均”的思路，有效地抵消了量子化学计算的起始结构偶然性带来的误差，比较准确地描述了较大的煤模型分子与较小的气体分子之间的作用，比较准确地描述了溶剂对煤中氢键以多种可能微观结构作用的结果。用量子化学密度泛函理论计算方法对煤模型分子的反应动力学进行了深入研究，建立了通过势能扫描计算高效率搜寻过渡态的方法，准确可靠地确定了煤化学中的几个重要反应的化学动力学机理：N-甲基吡咯烷酮和二硫化碳生成N-甲基吡咯烷-2-硫酮的动力学机理，更多还原

【Abstract】 The quantum chemistry calculation method has been gradually used to study the correlation between coal structure and reactivity in coal chemistry. The method has gradually formed a new research branch, and provided a feasible scheme for dealing with coal structure. How to choose and build an appropriate coal structure is a key issue for the application of quantum chemistry calculation method. It is a practical method to construct the Local Micro-Structure Model of Coal (LMSMC) for application of quantum chemistry calculation method to coal structure and reactivity.This dissertation presents the idea of constructing the different LMSMC for specific properties of coal and studying on correlation between coal structure and reactivity using quantum chemistry calculation method. Seven types of LMSMCs that could be used for quantum chemistry calculation are built: the fractional structure models describing thermal chemical properties of coal, the polycyclic aromatic compound models describing UV-Vis absorption properties of coal, the substituted polycyclic aromatic hydrocarbon edge models describing surface electric potential properties of coal, the fractional structure models describing gas adsorption on coal surface, the phenol hydroxyl self-associated model describing hydrogen bond in coal, the fixed structure models and optimized structure models describing the solvent extraction of coal. These types of models are used for quantum chemistry calculation to illustrate the relationship between the structures and properties.The idea of "Multipoint Calculation and Whole Average" was put forward, which effectively reduces the error resulting from the chance of using different initial structures in the process of quantum chemistry calculation. The result more accurately describes the interaction between larger coal model molecule更多还原