A computational study of CX (X = H, C, F, Cl) bond dissociation enthalpies (BDEs) in polyhalogenated methanes and ethanes
A computational study of CX (X = H, C, F, Cl) bond dissociation enthalpies (BDEs) in polyhalogenated methanes and ethanes
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DOI：
10.1002/poc.1704
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发表时间：
2011
影响因子：
1.8
通讯作者：
Jing Shi;Jian He;Hua-Jing Wang
中科院分区：
文献类型：
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作者：
Jing Shi;Jian He;Hua-Jing Wang
溴化二苯醚（BDEs）在氯氟烃（CFCs）和氢氯氟烃（HCFCs）的光解过程中起着重要作用，导致平流层臭氧的消耗。在这项工作中，我们估计的性能的密度泛函理论（DFT）方法计算的BDE的CFCs和HCFC的，并发现DFT是不可靠的，这个系统。最后总结了该系统中DFT方法不可靠的原因。此外，复合从头算方法G3和G3 B3被证明可以准确地估计多卤代低级烷烃的溴化二苯醚。对《化学键能综合手册》（2007年第2版）中的82个实验值进行了重新评价。其中8个被怀疑为理论值和实验值之间的偏差超过20.0 kJ/mol。我们还系统地预测了多卤代甲烷和乙烷中的溴化二苯醚。进一步研究了它们的结构与性能的关系。版权所有© 2010约翰威利父子有限公司.
Bond dissociation enthalpies (BDEs) play a significant role in the photolysis of Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which lead to the depletion of stratospheric ozone. In this work, we estimate the performance of Density Functional Theory (DFT) methods in calculating BDEs of CFCs and HCFCs, and find that DFTs are unreliable for this system. The reasons for the unreliability of DFT methods in this system are also concluded. Furthermore, composite ab initio methods G3 and G3B3 are demonstrated to accurately estimate BDEs of polyhalogenated lower alkanes. Eighty two experimental values from Comprehensive Handbook of Chemical Bond Energies (2007, 2nd edition) are re-evaluated. Eight of them are doubted as having a deviation exceeding 20.0 kJ/mol between the theoretical and experimental values. We also systematically predict the BDEs in polyhalogenated methanes and ethanes. A further study is conducted on their relationships of structures and properties. Copyright © 2010 John Wiley & Sons, Ltd.