• D J McGarvey

      Articles written in Journal of Chemical Sciences

    • The application of diffuse reflectance laser photolysis to study photochemistry at interfaces and in dyed fabrics

      F Wilkinson D J McGarvey D R Worrall

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      Recently we have extended to heterogeneous, opaque and often highly scattering systems, the application of flash photolysis by using diffuse reflected light instead of transmitted light as the analysing source on timescales extending from several seconds to picoseconds. Laser-induced transient spectra and decay kinetics have been observed from a wide variety of samples including fractions of monolayers of organic molecules adsorbed on catalytic metal oxide surfaces, within inorganic and organic microcrystals, from dyed fabrics and from paper pulp. The potential of the technique to study photochemical reactions at interfaces is demonstrated with particular reference to ion-electron recombination on porous silica surfaces and to photochemical and photophysical processes occurring in dyed fabrics.

    • Factors which determine the efficiency of sensitized singlet oxygen production

      F Wilkinson D J McGarvey A Olea

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      Nanosecond laser photolysis measurements of sensitized phosphorescence from oxygen have been used to obtain values for singlet oxygen formation efficiencies during oxygen quenching of excited singlet and triplet states of anthracene and naphthalene derivatives. Oxygen quenching of excited singlet states of anthracene and dicyanoanthracene in cyclohexane has been shown to lead to catalysed production of triplet states with unit efficiency in both cases, but concurrent production of singlet oxygen only occurs in the case of 9,10-dicyanoanthracene with efficiency close to unity whereas the efficiency for singlet oxygen production due to direct oxygen quenching of excited singlet anthracene is close to zero. In contrast to these results, oxygen quenching of the triplet states of anthracene and dicyanoanthracene in cyclohexane yields singlet oxygen with unit efficiency whereas the singlet oxygen formation efficiency during oxygen quenching of triplet 1-ethylnaphthalene is only 0.86 in cyclohexane and drops to 0.51 in acetonitrile. This solvent dependence demonstrates the role which charge transfer interactions play in determining singlet oxygen yields. Further information concerning the decay of excited oxygen-aromatic hydrocarbon charge-transfer complexes have been obtained from picosecond laser pump-probe studies where direct excitation is into the charge-transfer bands of oxygenated 1-ethylnaphthalene. Following the excitation of the charge-transfer complex, the triplet state of 1-ethylnaphthalene is rapidly produced with an efficiency which shows a marked solvent dependency, being 0.4 and 0.8 in acetonitrile and cyclohexane, respectively. The measured yields of singlet oxygen formation following excitation into 1-ethylnaphthalene-oxygen charge-transfer complexes are 0.36 and 0.78 in these two solvents which is greater than that expected on the basis of the measured triplet yields. Mechanisms of quenching of excited states by oxygen which explain these results are discussed.

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