Sandhiya Lakshmanan, Zipse Hendrik
Department of Chemistry, LMU München, München, D-81377, Germany.
J Comput Chem. 2017 Sep 30;38(25):2186-2192. doi: 10.1002/jcc.24870. Epub 2017 Jul 11.
OO bond homolysis in hydrogen peroxide (H O ) has been studied using theoretical methods of four conceptually different types: hybrid DFT (B3LYP, M06-2X), double-hybrid DFT (B2-PLYP), coupled-cluster (CCSD(T)), and multiconfigurational (CASPT2). In addition, the effects of basis set size have also been analyzed. For all of these methods, the OO bond homolysis in hydrogen peroxide has been found to proceed through hydrogen bonded radical pair complexes. Reaction barriers for collapse of the radical pairs to hydrogen peroxide are minute, leading to an overall very flat potential energy surface. However, hydrogen bonding energies in the radical pair complex expressed as the energy difference to two separate hydroxyl radicals are sizeable and exceed 10 kJ/mol for all theoretical methods considered in this study. © 2017 Wiley Periodicals, Inc.
已使用四种概念上不同类型的理论方法研究了过氧化氢（H₂O₂）中OO键的均裂：杂化密度泛函理论（B3LYP、M06 - 2X）、双杂化密度泛函理论（B2 - PLYP）、耦合簇理论（CCSD(T)）和多组态理论（CASPT2）。此外，还分析了基组大小的影响。对于所有这些方法，已发现过氧化氢中OO键的均裂通过氢键自由基对络合物进行。自由基对分解为过氧化氢的反应势垒很小，导致整体势能面非常平坦。然而，以与两个单独的羟基自由基的能量差表示的自由基对络合物中的氢键能相当大，对于本研究中考虑的所有理论方法，均超过10 kJ/mol。© 2017威利期刊公司。
