Nature of the thiyl peroxy radical. ESR and ab initio MO evidence for intermolecular stabilization of the charge transfer state RS{sup +}OO{center_dot}{minus}

Journal Article · Thu May 18 00:00:00 EDT 1995 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/j100020a023· OSTI ID:62300

Razskazovskii, Y; Colson, A O; Sevilla, M D ^[1]

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1. Oakland Univ., Rochester, MI (United States)

This work presents experimental evidence that the unusual properties of the thiyl peroxyl radical result from specific nucleophilic solvation of sulfur, which stablizes the charge transfer state, RS{sup +}OO{sup *-}. We find that theoretical MO calculations can mimic this state by association of a negative ion, X{sup -}, with the sulfur atom. Our experimental results show that in the poorly solvating medium, freon, the spin density distribution of the tert-butyl-SOO species is quite different from that found in an aqueous or polar solvent and approaches the spin density distribution in a typical peroxyl radical. 36 refs., 6 figs., 3 tabs.

• Sponsoring Organization: USDOE
• OSTI ID: 62300
• Journal Information: Journal of Physical Chemistry, Vol. 99, Issue 20; Other Information: PBD: 18 May 1995
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
66 PHYSICS
RADICALS
ELECTRON SPIN RESONANCE
ULTRAVIOLET RADIATION
MOLECULES
SULFUR
OXYGEN
ATOMS
HYPERFINE STRUCTURE
COMPILED DATA