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Sandhiya, Lakshmanan; Zipse, Hendrik (2017): OO bond homolysis in hydrogen peroxide. In: Journal of Computational Chemistry, Vol. 38, No. 25: pp. 2186-2192
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OO bond homolysis in hydrogen peroxide (H2O2) 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. (c) 2017 Wiley Periodicals, Inc.