【作者】 张通；

【导师】 曾凡桂；

【作者基本信息】 太原理工大学 ， 采矿工程， 2005， 硕士

【摘要】 煤分子间相互作用和分子识别是煤超分子化学的关键所在。通过对煤分子间相互作用的理论计算研究,可以帮助了解煤超分子间分子识别的机制,进而揭示煤结构的超分子化学特征,从而丰富煤结构理论和为煤分子工程学的发展提供理论基础。本文应用量子化学理论方法计算研究了煤分子间相互作用。 采用HF、MP2方法在6-31G~*基组下,研究了羟基自缔合氢键垂直和平行两种构型,通过能量分析,得出垂直构型比平行构型稳定,其在6-311G/RHF,MP2方法下计算并经过基组迭加误差校正得到的分子间相互作用能为-10.80KJ/mol,说明该氢键是一个相对较弱的氢键体系。 采用HF、MP2方法在6-31G+基组下,对煤中几类氢键进行研究,求得它们的优化构型,通过能量分析和热力学分析,得到一致的氢键稳定顺序:环状羟基紧密缔合氢键>羟基-氮氢键>羟基醚氧氢键>自缔合羟基氢键>羟基-π氢键。 在DFT-B3LYP/6-31G+水平下,对π—π堆积相互作用进行计算研究,求得平行优化构型在6-31G(d,p)单点能计算得更多还原

【Abstract】 The intermolecular interactions a nd m olecular recognition of coal are key components of coal supramolecular chemistry. By the theoretic studies on intermolecular interactions of coal molecular, we may understand the m olecular recognition mechanism of coal supramolecular molecules, and then disclosure the characterization of coal supramolecular molecules, to supply theoretical basis for the abundance of coal structural theory and the development of coal molecular engineering subject. We study the coal intermolecular interactions by quantum chemistry theoretic methods in this paper.The parallel and T-shaped configurations of OH self-associated hydrogen bond is studied by ab intio HF method at 6-31*basis set. The T-shaped optimized configuration is more stable than parallel optimized configuration by energy analysis, and its energy is -10.80kj/mol by 6-311G/RHF,MP2 method and BSSE corrected. The r esult s hows t his h ydrogen b ond isaw eakly h ydrogen b ond system.The hydrogen bond in coal is studied by HF/MP2 method on 6-31G+ basis set, and get their optimized configurations. These hydrogen bonds accept the same stable order after energy and thermodynamic analysis, that is cyclic OH hydrogen bond > OH-N hydrogen bond > OH-ether hydrogen bond > OH self-associated > OH- hydrogen bond.The - stacking interactions are studied by DFT method on B3LYP/6-31G+ level, and get result of energy of parallel optimized configuration is -16.87kj/mol by single-point energy computing on 6-31G(d,p) basis set, and the system intermolecular interactions is relatively weak.The intermolecular interactions of coal big molecularconstruction unit are researched by theoretic study on DFT-B3LYP/3-21G level, and get the intermolecular interactional energy is -61.05kj/mol on 6-31G basis set. The energy shows that this intermolecular interactions is relatively weak.更多还原