Excimer formation in the photochemistry of aliphatic ketones I: concentration dependence of quantum yields

L. Biczók, T. Bérces, S. Förgeteg, F. Márta

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Abstract

The photochemistry of 2-pentanone was studied in iso-octane at 313 nm. The quantum yields of the Norrish type I and II primary processes were found to increase with increasing ketone concentration and to attain limiting values at high concentrations (above about 0.3 mol dm-3. The triplet yield, studied by means of the sensitized biacetyl phosphorescence technique, showed a similar concentration dependence. The enhancement of singlet → triplet intersystem crossing by ground state ketone molecules was interpreted by assuming singlet excimer formation. The excimer may redissociate into singlet state and ground state ketone molecules or may enter intersystem crossing followed by dissociation of the excimer triplet state. Evaluation of the experimental results yielded rate coefficients for the first-order intersystem crossing step and for the type II decomposition from the triplet state.

Original languageEnglish
Pages (from-to)41-48
Number of pages8
JournalJournal of Photochemistry
Volume27
Issue number1
DOIs
Publication statusPublished - 1984

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Photochemical reactions
Quantum yield
Ketones
Ground state
Diacetyl
Phosphorescence
Molecules
Decomposition

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Excimer formation in the photochemistry of aliphatic ketones I : concentration dependence of quantum yields. / Biczók, L.; Bérces, T.; Förgeteg, S.; Márta, F.

In: Journal of Photochemistry, Vol. 27, No. 1, 1984, p. 41-48.

Research output: Contribution to journalArticle

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abstract = "The photochemistry of 2-pentanone was studied in iso-octane at 313 nm. The quantum yields of the Norrish type I and II primary processes were found to increase with increasing ketone concentration and to attain limiting values at high concentrations (above about 0.3 mol dm-3. The triplet yield, studied by means of the sensitized biacetyl phosphorescence technique, showed a similar concentration dependence. The enhancement of singlet → triplet intersystem crossing by ground state ketone molecules was interpreted by assuming singlet excimer formation. The excimer may redissociate into singlet state and ground state ketone molecules or may enter intersystem crossing followed by dissociation of the excimer triplet state. Evaluation of the experimental results yielded rate coefficients for the first-order intersystem crossing step and for the type II decomposition from the triplet state.",
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AU - Márta, F.

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