Theoretical Studies on the Molecular Structures and Thermodynamic Properties of Polychlorinated Fluoranthenes

• 作者: WANG Hong-Jun WANG Hui-Juan WANG Yan ZENG Xiao-Lan
• 来源期刊: 结构化学
• 学科: 化学
• 关键词: 多氯联苯 热力学性质 分子结构 Gibbs自由能 标准生成焓 吉布斯自由能 热力学稳定性 相对稳定
• 年，卷（期）: 2012,（4）
• 页码范围: 539-549
• 页数: 11页
• 分类号: O623.11|X132
• 语种: 英文

摘要

DFT-B3LYP/6-311G** method has been used to optimize molecular geometric structures of 527 polychlorinated fluoranthene(PCFRT) congeners and calculate their thermo-dynamic properties in the ideal gas state,such as heat capacity at constant volume(Cv),entropy(S),standard enthalpy of formation(ΔfH) and standard Gibbs free energy of formation(ΔfG).The relations of Cv,S,ΔfH and ΔfG with the number and position of chlorine atoms have also been explored,from which the relative stability of PCFRT congeners was theoretically proposed according to the magnitude of the relative standard Gibbs free energy of formation(Δr,fG).It was found that some of the PCFRT isomers are in a nonplanar configuration and there are intramolecular Cl…Cl weak interactions in some of the isomers.With increasing the number of chlorine atoms,the values of ΔfH and ΔfG of the most stable PCFRT isomers decrease initially and then increase.The values of ΔfH and ΔfG of PCFRT congeners with the same number of chlorine atoms show a strong dependence on the positions of chlorine atoms.The relative thermodynamic stability of PCFRT isomers is determined mainly by intramolecular adjacent Cl…Cl nuclear repulsive interaction between Cl atoms at two different six-membered rings.Most PCFRT congeners are easier to form thermodynamically than their parent compound.

作者信息

序号	姓名	单位	发文数	被引次数	H指数	G指数
1	ZENG Xiao-Lan		1	0	0.0	0.0
2	WANG Hong-Jun		1	0	0.0	0.0
3	WANG Yan		1	0	0.0	0.0
4	WANG Hui-Juan		1	0	0.0	0.0