XO(2)、X(2)O、XYO、X(2)O(2)和 XY(2)O(2)（X、Y = Cl、Br 和 I）异构体的热力学性质。

Thermodynamic properties of the XO(2), X(2)O, XYO, X(2)O(2), and XYO(2) (X, Y = Cl, Br, and I) isomers.

机构信息

Chemistry Department, The University of Alabama, Shelby Hall, Box 870336, Tuscaloosa, Alabama 35487-0336, USA.

出版信息

J Phys Chem A. 2010 Apr 1;114(12):4254-65. doi: 10.1021/jp911320p.

PMID:20187618

Abstract

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 BrBrO(2), IIO(2), ClBrO(2), ClIO(2), and BrIO(2) isomers, as well as various molecules involved in the bond dissociation processes. Of the BrBrO(2) isomers, BrOOBr is predicted to be the most stable by 8.5 and 9.3 kcal/mol compared to BrBrO(2) 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 BrBrO(2), 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 IIO(2) isomers, IIO(2) 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 IIO(2) 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.

摘要

已经在耦合簇水平上进行了高级从头算电子结构计算，并对三重态进行了修正，将其外推至完全基组极限，以研究 BrBrO(2)、IIO(2)、ClBrO(2)、ClIO(2)和 BrIO(2)异构体以及各种涉及键离解过程的分子的热力学。在 BrBrO(2)异构体中，与 BrBrO(2)和 BrOBrO 相比，BrOOBr 在 298 K 时分别预测为最稳定的，稳定度高出 8.5 和 9.3 kcal/mol。在 BrOOBr 中最弱的键是 O-Br 键，键离解能 (BDE) 为 15.9 kcal/mol，而在 BrBrO(2)中最弱的键是 Br-Br 键，BDE 为 19.1 kcal/mol。在 BrOBrO 中最小的 BDE 是中心 O-Br 键，BDE 为 12.6 kcal/mol。在 IIO(2)异构体中，与 IOIO、IOOI 和 OIIO 相比，在 298 K 时，IIO(2)分别预测为最稳定的，稳定度高出 3.3、9.4 和 28.9 kcal/mol。在 IIO(2)中最弱的键是 I-I 键，BDE 为 22.2 kcal/mol。在 IOIO 和 IOOI 中最小的 BDE 是末端 O-I 键，分别为 19.0 和 5.2 kcal/mol。