The Stability of α‐Hydroperoxyalkyl Radicals |
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| Authors: | Dr Josep M Anglada Dr Ramon Crehuet Prof Joseph S Francisco |
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| Affiliation: | 1. College of Arts and Sciences, University of Nebraska-Lincoln, Lincoln, NE, United States;2. Departament de Química Biològica i Modelització Molecular, IQAC—CSIC, Barcelona, Spain |
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| Abstract: | High‐level ab initio and Born–Oppenheimer molecular dynamic calculations have been carried out on a series of hydroperoxyalkyl (α‐QOOH) radicals with the aim of investigating the stability and unimolecular decomposition mechanism into QO+OH of these species. Dissociation was shown to take place through rotation of the C?O(OH) bond rather than through elongation of the CO?OH bond. Through the C?O(OH) rotation, the unpaired electron of the radical overlaps with the electron density on the O?OH bond, and from this overlap the C=O π bond forms and the O?OH bond breaks spontaneously. The CH2OOH, CH(CH3)OOH, CH(OH)OOH, and α‐hydroperoxycycloheptadienyl radical were found to decompose spontaneously, but the CH(CHO)OOH has a decomposition energy barrier of 5.95 kcal mol?1 owing to its steric and electronic features. The systems studied in this work provide the first insights into how structural and electronic effects govern the stabilizing influence on elusive α‐QOOH radicals. |
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| Keywords: | ab initio calculations atmospheric chemistry density functional calculations molecular dynamics radicals |
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