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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (10): 1139-1150.    下一篇

研究论文

多氯二苯硫醚结构参数和热力学性质的密度泛函理论研究

朱红薇1，江建林2，王遵尧*,2，王连生3，于红霞3   

  1. (1复旦大学药学院 上海 200032)
    (2嘉兴学院生物与化学工程学院 嘉兴 314001)
    (3南京大学环境学院 南京 210093)
  • 投稿日期:2007-11-27 修回日期:2008-01-17 发布日期:2008-05-28
  • 通讯作者: 王遵尧

DFT Study on the Structural Parameters and Thermodynamic Properties of Polychlorinated Diphenyl Sulfides

ZHU, Hong-Wei1, JIANG, Jian-Lin2, WANG, Zun-Yao*,2, WANG, Lian-Sheng3, YU, Hong-Xia3   

  1. (1 School of Pharmacy, Fudan University, Shanghai 200032)
    (2Department of Biological and Chemical Engineering, Jiaxing University, Jiaxing 314001)
    (3Department of Environment, Nanjing University, Nanjing 210093)
  • Received:2007-11-27 Revised:2008-01-17 Published:2008-05-28
  • Contact: WANG, Zun-Yao

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862

被引次数

21

在B3LYP/6-31G*水平上对209个多氯二苯硫醚(PCDS)系列化合物进行了全优化计算, 得到各分子的结构参数和热力学参数. 研究了这些参数与氯原子在苯环各位置的取代数目和相互位置(NPCS)之间的关系发现: 分子平均极化率(α)、焓(H $)、自由能(G $)、恒容热容( )和熵(S $)与NPCS之间有很强的相关性, 相关性系数r2＞0.988, 分子体积(Vm)、最高占据轨道能(EHOMO)和最低未占据轨道能(ELUMO)与NPCS也有较好的相关性, 相关性系数r2分别为0.949, 0.894和0.915. 设计等键反应, 计算了PCDS各异构体的标准生成热(ΔfH $)和标准生成自由能(ΔfG $). 根据异构体自由能的相对大小, 求得异构体的相对稳定性顺序.

关键词: 多氯二苯硫醚, 密度泛函理论, 氯原子取代位置方法, 结构参数, 热力学性质, 相对稳定性

Fully optimized calculation and frequency analysis of 209 polychlorinated diphenyl sulfide (PCDS) compounds were carried out at the B3LYP/6-31G* level and their structural and thermodynamic parameters were obtained. The relation of these parameters with the number and relative positions of Cl atom substitution (NPCS) was studied, and it was found that there exists high correlation between the molecular mean polarizability (α), enthalpy (H $), free energy (G $), heat capacity at constant volume ( ) or entropy (S $) and NPCS (correlative coefficients r2＞0.988). It was also found that the molecular volume (Vm), the energy of highest occupied molecular orbital (EHOMO) and the energy of lowest unoccupied molecular orbital (ELUMO) had good correlation with NPCS and the correlative coefficients r2 were 0.949, 0.894 and 0.915 respectively. The isodesmic reactions were designed to calculate standard enthalpy of formation (ΔfH $) and standard free energy of formation (ΔfG $) of PCDS congeners. The order of relative stability of these PCDS congeners was theoretically proposed based on the relative magnitude of their ΔfG .

Key words: polychlorinated diphenyl sulfide, DFT method, position of Cl atom substitution method, structural parameter, thermodynamic property, relative stability