title: Computational study on the existence of organic peroxy radical-water complexes (RO2.H2O).
abstract: The existence of a series of organic peroxy radical-water complexes [CH3O2.H2O (methyl peroxy); CH3CH2O2.H2O (ethyl peroxy); CH3C(O)O2.H2O (acetyl peroxy); CH3C(O)CH2O2.H2O (acetonyl peroxy); CH2(OH)O2.H2O (hydroxyl methyl peroxy); CH2(OH)CH2O2.H2O (2-hydroxy ethyl peroxy); CH2(F)O2.H2O (fluoro methyl peroxy); CH2(F)CH2O2.H2O (2-fluoro ethyl peroxy)] is evaluated using high level ab initio calculations. A wide range of binding energies is predicted for these complexes, in which the difference in binding energies can be explained by examination of the composition of the R group attached to the peroxy moiety. The general trend in binding energies has been determined to be as follows: fluorine approximately alkyl < carbonyl < alcohol. The weakest bound complex, CH3O2.H2O, is calculated to be bound by 2.3 kcal mol-1, and the strongest, the CH2(OH)O2.H2O complex, is bound by 5.1 kcal mol-1. The binding energy of the peroxy radical-water complexes which contain carbonyl and alcohol groups indicates that these complexes may perturb the kinetics and product branching ratios of reactions involving these complexes.
authors.affiliation: Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, USA.
authors.forename: Jared
authors.initials: J
authors.lastname: Clark
authors.forename: Alecia M
authors.initials: AM
authors.lastname: English
authors.forename: Jaron C
authors.initials: JC
authors.lastname: Hansen
authors.forename: Joseph S
authors.initials: JS
authors.lastname: Francisco
mesh_terms: D003198:Computer Simulation; D005609:Free Radicals / Q000737:chemistry; D006860:Hydrogen Bonding; D008956:Models, Chemical; D010545:Peroxides / Q000737:chemistry*; D011789:Quantum Theory; D014867:Water / Q000737:chemistry*
chemical_list: D005609:Free Radicals; D010545:Peroxides; D014867:Water