Thermodynamic Properties of the XO2, X2O, XYO, X2O2, and XYO2 (X, Y = Cl, Br, and I) Isomers

详细信息    查看全文

• 作者：Daniel J. Grant ; Edward B. Garner ; III ; Myrna H. Matus ; Minh Tho Nguyen ; Kirk A. Peterson ; Joseph S. Francisco ; David A. Dixon
• 刊名：Journal of Physical Chemistry A
• 出版年：2010
• 出版时间：April 1, 2010
• 年：2010
• 卷：114
• 期：12
• 页码：4254-4265
• 全文大小：258K
• 年卷期：v.114,no.12(April 1, 2010)
• ISSN：1520-5215

文摘

High level ab initio electronic structure calculations at the coupled cluster level with a correction for triples extrapolated to the complete basis set limit have been made for the thermodynamics of the BrBrO₂, IIO₂, ClBrO₂, ClIO₂, and BrIO₂ isomers, as well as various molecules involved in the bond dissociation processes. Of the BrBrO₂ isomers, BrOOBr is predicted to be the most stable by 8.5 and 9.3 kcal/mol compared to BrBrO₂ and BrOBrO at 298 K, respectively. The weakest bond in BrOOBr is the O−Br bond with a bond dissociation energy (BDE) of 15.9 kcal/mol, and in BrBrO₂, it is the Br−Br bond of 19.1 kcal/mol. The smallest BDE in BrOBrO is for the central O−Br bond with a BDE of 12.6 kcal/mol. Of the IIO₂ isomers, IIO₂ is predicted to be the most stable by 3.3, 9.4, and 28.9 kcal/mol compared to IOIO, IOOI, and OIIO at 298 K, respectively. The weakest bond in IIO₂ is the I−I bond with a BDE of 22.2 kcal/mol. The smallest BDEs in IOIO and IOOI are the terminal O−I bonds with values of 19.0 and 5.2 kcal/mol, respectively.