醛酮类化合物的分子力场参数推导及热力学性质计算ForceField.PDFVIP

2009 年第 67 卷 化 学 学 报 Vol. 67, 2009 第 23 期, 2669～2677 ACTA CHIMICA SINICA No. 23, 2669～2677 ·研究论文· 醛酮类化合物的分子力场参数推导及热力学性质计算 王 玲 李晓锋 赵立峰 孙 淮* (上海交通大学化学化工学院 上海 200240) 摘要 针对醛酮类分子, 基于第一原理的量子化学计算结果开发了准确、可迁移的全原子力场. 利用所得到的力场, 采 用分子动力学和蒙特卡罗方法对醛酮类分子的气相分子结构、振动频率、构象能和凝聚相液体性质(密度和蒸发焓), 以 及流体的多种热力学性质包括气液相平衡和临界性质, 与涨落相关的等压热容, 传递性质如剪切粘度等进行了计算和 预测. 计算结果表明, 该力场可准确地反映气相分子的结构、振动频率、构象能和凝聚相液体密度和蒸发焓等性质, 并 准确地预测一系列醛酮类分子的多种热力学性质. 所开发的醛酮类分子力场函数形式简单, 并具有良好的可迁移性和 准确性, 在应用范围和计算精度上都有明显的改善和提高. 关键词 第一性原理; 分子力学力场; 醛酮; 热力学性质 Force Field Development and Predictions of Thermodynamic Properties for Aldehydes and Ketones Wang, Ling Li, Xiaofeng Zhao, Lifeng Sun, Huai* (School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240) Abstract A novel transferable and accurate all atom force field was developed for aldehyde and ketone molecules, which was based on the first principle calculations. The force field was applied successfully to predict gas phase properties, condensed phase properties, and liquid thermodynamic properties. The gas phase properties included molecular structures, conformation energies and vibration frequencies. The con- densed phase properties included liquid density and heat of vaporization. The thermodynamic properties in- cluded vapor-liquid and critical properties, fluctuation related properties such as constant pressure heat ca- pacity, transport properties such