Effect of solvent on the rate constant for the radiative deactivation of singlet molecular oxygen (1.DELTA.gO2)

Relative rate constants for the radiative deactivation (k/sub r/) of singlet molecular oxygen (/sup 3/Sigma/sub g//sup -/O/sub 2/ reverse arrow /sup 1/..delta../sub g/O/sub 2/) have been determined in 15 solvents. A substantial solvent effect is observed. Changes in the value of k/sub r/ can exceed...

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Veröffentlicht in:	J. Phys. Chem.; (United States) 1987-08, Vol.91 (17), p.4599-4602
Hauptverfasser:	Scurlock, Rodger D, Ogilby, Peter R
Format:	Artikel
Sprache:	eng
Schlagworte:	400500 - Photochemistry ACETONE ACETONITRILE ALCOHOLS ALKANES ALKYLATED AROMATICS AROMATICS BENZENE BROMINATED AROMATIC HYDROCARBONS CARBON COMPOUNDS CARBON SULFIDES CHALCOGENIDES CHEMICAL REACTION KINETICS CHEMICAL REACTIONS CHEMISTRY CHLORINATED AROMATIC HYDROCARBONS CYCLOALKANES CYCLOHEXANE DATA ELECTRONIC STRUCTURE ELEMENTS ENERGY-LEVEL TRANSITIONS Exact sciences and technology EXPERIMENTAL DATA FLUORINATED AROMATIC HYDROCARBONS General and physical chemistry HALOGENATED AROMATIC HYDROCARBONS HYDROCARBONS HYDROXY COMPOUNDS INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY IODINATED AROMATIC HYDROCARBONS KETONES KINETICS NITRILES NONMETALS NUMERICAL DATA ORGANIC BROMINE COMPOUNDS ORGANIC CHLORINE COMPOUNDS ORGANIC COMPOUNDS ORGANIC FLUORINE COMPOUNDS ORGANIC HALOGEN COMPOUNDS ORGANIC IODINE COMPOUNDS ORGANIC NITROGEN COMPOUNDS OXYGEN PHOTOCHEMICAL REACTIONS PHOTOCHEMISTRY Physical chemistry of induced reactions (with radiations, particles and ultrasonics) PROPANOLS REACTION KINETICS SOLVENT PROPERTIES SULFIDES SULFUR COMPOUNDS TOLUENE
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Zusammenfassung:	Relative rate constants for the radiative deactivation (k/sub r/) of singlet molecular oxygen (/sup 3/Sigma/sub g//sup -/O/sub 2/ reverse arrow /sup 1/..delta../sub g/O/sub 2/) have been determined in 15 solvents. A substantial solvent effect is observed. Changes in the value of k/sub r/ can exceed a factor of 20. A reasonably good correlation exists between the solvent polarizability, defined as a function of the solvent refractive index, and the radiative rate constant. We suggest that our data support a model in which /sup 1/..delta../sub g/O/sub 2/ is perturbed through the formation of a discrete oxygen-solvent collision complex.
ISSN:	0022-3654 1541-5740
DOI:	10.1021/j100301a034