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OO bond homolysis in hydrogen peroxide
Author(s) -
Sandhiya Lakshmanan,
Zipse Hendrik
Publication year - 2017
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24870
Subject(s) - homolysis , radical , chemistry , hydrogen peroxide , hydrogen bond , potential energy surface , peroxide , bond dissociation energy , bond energy , photochemistry , computational chemistry , molecule , organic chemistry , dissociation (chemistry)
OO bond homolysis in hydrogen peroxide (H 2 O 2 ) 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.