Radiative and non-radiative decay rates of alkyl substituted diacetylene cations at selected energies within their 2 Ā states determined via photoelectron-photon coincidence measurements
1981; Elsevier BV; Volume: 59; Issue: 1-2 Linguagem: Inglês
10.1016/0301-0104(81)80088-2
ISSN1873-4421
AutoresP. Förster, John P. Maier, Fritz Thommen,
Tópico(s)Molecular spectroscopy and chirality
ResumoAbstract Fluorescence quantum yields and cacade-free lifetimes of the cations of 1,3-pentadiyne, of 2,4-hexadiyne and of four of their deuterated derivatives as well as of 1,3-hexadiyne have been determined at selected energies within their 2 Ā(π −1 ) states. These data were obtained under collision-free conditions by means of the photoelectron-photon coincidence technique using He(Iα), or Ne(I) as the photoionisation source. The rate constants of the radiative ( 2 Ā→ 2 X¯), and non-radiative ( 2 2 ℝX¯) channels could therefore be inferred as a function energy. The non-radiative rates increase with excess energy and vary among the isotopic species. For these cations the non-radiative pathway leads to fragment ions. The implications of the reported results are discussed.
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