多溴二苯并噻吩系列化合物的热力学性质及稳定性的密度泛函理论  

Thermodynamic properties of polybrominated dibenzothiophenes by density functional theory

作　　者：庞泉德[1] 胡仰栋[1] 伍联营[1] 欧阳旭[1] 张伟涛[1] 夏红卫[1] 

机构地区：[1]中国海洋大学化学化工学院,山东青岛266100

出　　处：《计算机与应用化学》2009年第11期1393-1398,共6页Computers and Applied Chemistry

基　　金：国家自然科学基金资助项目(20376078)

摘　　要：本文在298.15 K和1.013×10~5Pa时,根据密度泛函理论(DFT),使用Gaussian 03程序,在B3LYP/6-31G(d)水平上计算117个多溴二苯噻吩系列化合物(PBDTs),得各分子的热力学性质。设计等键反应,计算PBDTs系列化合物的标准生成热Δ_fH^(?)和标准生成自由能Δ_fG^(?)。同时用程序Origin7.5将这些热力学参数与溴原子的取代位置及取代数目线性回归,求出相关方程,研究表明:热力学参数、标准生成热、标准生成自由能与溴原子的取代位置及取代数目之间关系极密切。根据标准生成自由能的相对大小,本文从理论上求得该化合物异构体的相对稳定性顺序。本文研究该化合物热力学性质及其稳定性,对于研究其生成、降解以及对环境的潜在威胁具有重要意义。The thermodynamic properties of 117 polybrominated dibenzothiophenes （PBDTs） in the ideal gas state at 298. 15 K and 1. 013 × 10^5 Pa were calculated at the B3L YP/6-31G（d） level using Gaussian 03 program and their thermodynamic properties were obtained. The isodesmic reactions were designed to calculate standard enthalpy of formation and standard free energy of formation of PBDTs congeners. The relations of these thermodynamic properties with the number and position of Br atom substitution were discussed, and it was found that there existed high correlation between thermodynamic properties （ standard enthalpy of formation and standard free energy of formation） and number and position of Br atom substitution. On the basis of the relative magnitude of their standard free energy of formation, the order of relative stability of PBDT congeners was theoretically proposed.

关 键 词：多溴二苯并噻吩PBDT 溴原子取代位置和数目 密度泛函理论DFF 热力学性质 相对稳定性 

分 类 号：TQ015.9[化学工程] O6-39[理学—化学]